Supported nonmetallocene catalyst, preparation and use thereof

ABSTRACT

This invention relates to a supported nonmetallocene catalyst and preparation thereof. The supported nonmetallocene catalyst can be produced with a simple and feasible process and is characterized by an easily controllable polymerization activity. This invention further relates to use of the supported nonmetallocene catalyst in olefin homopolymerization/copolymerization, which is characterized by a lowered assumption of the co-catalyst as compared with the prior art.

TECHNICAL FIELD

The present invention relates to a nonmetallocene catalyst.Specifically, this invention relates to a supported nonmetallocenecatalyst, preparation thereof and use thereof in olefinhomopolymerization/copolymerization.

BACKGROUND ART

The nonmetallocene catalyst, also called as the post-metallocenecatalyst, was discovered in middle and late 1990's, whose central atominvolves nearly all of the transition metal elements. The nonmetallocenecatalyst is comparative to, or exceeds, the metallocene catalyst in someaspects of the performance, and has been classified as the fourthgeneration catalyst for olefin polymerization, following the Zieglercatalyst, the Ziegler-Natta catalyst and the metallocene catalyst.Polyolefin products produced with such catalysts exhibit favorableproperties and boast low production cost. The coordination atom of thenonmetallocene catalyst comprises oxygen, nitrogen, sulfur and phosphor,without containing a cyclopentadiene group or a derivative thereof (forexample, an indene group or a fluorene group). The nonmetallocenecatalyst is characterized in that its central atom shows comparativelystrong electrophilicity and has a cis alkyl metal type or a metal halidetype central structure, which facilitates olefin insertion and σ-bondtransfer. Therefore, the central atom is easily subject to alkylation,and therefore facilitates formation of a cationic active center. Thethus formed complex has a restricted geometrical configuration, and isstereoselective, electronegative and chiral adjustable. Further, theformed metal-carbon bond is easy to be polarized, which furtherfacilitates homopolymerization and copolymerization of an olefin. Forthese reasons, it is possible to obtain an olefin polymer having acomparatively high molecular weight, even under a comparatively highpolymerization temperature.

However, it is known that in the olefin polymerization, the homogeneousphase catalyst suffers from such problems as short service life,fouling, high consumption of methyl aluminoxane, and undesirably low orhigh molecular weight in the polymer product, and thus only findslimited use in the solution polymerization process or the high-pressurepolymerization process, which hinders its wider application in industry.

Chinese patent Nos. 01126323.7, 02151294.9 and 02110844.7, andWO03/010207 disclose a catalyst or catalyst system finding a broadapplication in olefin polymerization. However, the catalyst or catalystsystem should be accompanied by a comparatively high amount ofco-catalysts, to achieve an acceptable olefin polymerization activity.Further, the catalyst or catalyst system suffers from such problems asshort service life and fouling.

It is normal to support the nonmetallocene catalyst by a certainprocess, so as to improve the performance of the catalyst in thepolymerization and the particle morphology of the polymer products. Thisis reflected by, moderate reduction of the initial activity of thecatalyst, elongation of the serve life of the catalyst, alleviation orelimination of caking or flash reaction during the polymerization,improvement of the polymer morphology, and increase of the apparentdensity of the polymer, thus extending its use to other polymerizationprocesses, for example, the gas phase polymerization or the slurrypolymerization.

Aiming at the catalysts of the Chinese patent Nos. 01126323.7,02151294.9 and 02110844.7, and WO03/010207, Chinese patent applicationLaid-Open Nos. CN1539855A, CN1539856A, CN1789291A, CN1789292A andCN1789290A, and WO2006/063501, and Chinese application patent No.200510119401.x provide several ways to support same catalyst on acarrier so as to obtain a supported nonmetallocene catalyst. However,each of these applications relates to the technology of supporting atransition metal-containing nonmetallocene organic metallic compound ona treated carrier, which necessarily involves complicate preparationsteps.

Most of the prior art olefin polymerization catalysts are metallocenecatalyst-based, for example, those according to U.S. Pat. No. 4,808,561and U.S. Pat. No. 5,240,894, Chinese patent application Laid-Open Nos.CN1344749A, CN1126480A, CN1307594A, CN1103069A, and CN1363537A, and U.S.Pat. No. 6,444,604, EP 0685494, U.S. Pat. No. 4,871,705 and EP0206794,and Chinese patent No. 94101358.8. Again, all of these applicationsrelate to the technology of supporting a transition metal-containingmetallocene catalyst on a treated carrier.

Chinese patent No. 200610026765.8 discloses a single site Zeigler-Nattacatalyst for olefin polymerization. In this catalyst, a coordinationgroup-containing salicylaldehyde or substituted salicylaldehydederivative is used as the electron donor. The catalyst is produced byintroducing a pre-treated carrier (for example, silica), a metalliccompound (for example, TiCl4) and the electron donor into a magnesiumcompound (for example, MgCl2)/tetrahydrofuran solution and thenpost-treating the resultant.

Chinese patent No. 200610026766.2 is similar to this patent, and relatesto an organic compound containing a hetero atom and use thereof forproducing a Zeigler-Natta catalyst.

However, the prior art supported nonmetallocene catalyst generallysuffers from the problem that if silica or a composite containing silicais used as the carrier for a nonmetallocene catalyst, this will bebeneficial to the particle morphology of the resultant polymer, butsilica suitable for this supporting purpose is rather expensive in cost,and has to be thermally activated or chemically activated before use,which necessitates complicate processing.

The magnesium compound is characterized by a low cost if used as thecarrier for a catalyst. Further, there is strong inter-reaction betweenthe magnesium compound and the active metals in a nonmetallocene complexand may easily lead to a supported nonmetallocene catalyst having ahigher activity.

Chinese patent Nos. 200710162667.1 and CN200710162676.0 andPCT/CN2008/001739 disclose a supported nonmetallocene catalyst andpreparation thereof, wherein a magnesium compound (for example magnesiumhalide, alkyl magnesium, alkoxyl magnesium, alkyl alkoxyl magnesium), amodified magnesium compound by chemically treating (by for example alkylaluminum, alkoxy aluminum) the magnesium compound, or a modifiedmagnesium compound by precipitating a magnesiumcompound-tetrahydrofuran-alcohol system is used as the carrier, andcontacts with a nonmetallocene ligand and an active metal compound indifferent orders one after another to perform an in-situ supportingprocess. The nonmetallocene ligand is an organic compound, which has nometal active center in it and shows no activity for olefinpolymerization, however will be given said activity after forming anorganic metallic compound with a chemical treating agent by an in-situreaction and given the ability to affect the polymerization performanceof the catalyst and the properties of the resultant polymer product.Further, the composition of the resultant catalyst does not necessarilycorrespond to that fed to the reaction, and deviation between differentbatches in product quality occurs. Further, the in-situ process goesmuch more violent than a direct-supporting process, and this may lead todestruction of the already-formed structure of the carrier during thereaction there between, and lead to poor particle morphology of theresultant polymer.

Therefore, there still exists a need for a supported nonmetallocenecatalyst, which can be produced in a simple way and in an industrialscale, free of the problems associated with the prior art supportednonmetallocene catalyst.

SUMMARY OF THE INVENTION

Upon in-depth study of the prior art, the present inventors found that asupported nonmetallocene catalyst produced by using a specific processcan solve the problems identified as aforesaid, whereby achieving thisinvention.

According to this invention, the present process for producing asupported nonmetallocene catalyst can be conducted in the absence of anyproton donor or any electron donor (for example, di-ether compoundsconventionally used in this field for this purpose), without the need ofsevere reaction requirements and reaction conditions. For these reasons,the present process is simple and suitable for industrial application.

Specifically, this invention generally relates to the first to fourthembodiments as follows.

The first embodiment relates to a process for producing a supportednonmetallocene catalyst, which comprises the steps of: dissolving amagnesium compound and a nonmetallocene complex in a solvent, to obtaina magnesium compound solution; and drying the magnesium compoundsolution to obtain the supported nonmetallocene catalyst.

The second embodiment relates to a process for producing a supportednonmetallocene catalyst, which comprises the steps of: dissolving amagnesium compound and a nonmetallocene complex in a solvent, to obtaina magnesium compound solution; and introducing into the magnesiumcompound solution a precipitating agent to obtain the supportednonmetallocene catalyst.

The third embodiment relates to a process for producing a supportednonmetallocene catalyst, which comprises the steps of: dissolving amagnesium compound and a nonmetallocene complex in a solvent, to obtaina magnesium compound solution; drying the magnesium compound solution toobtain a modified carrier; and treating the modified carrier with achemical treating agent selected from the group consisting of Group IVBmetal compounds to obtain the supported nonmetallocene catalyst.

The fourth embodiment relates to a process for producing a supportednonmetallocene catalyst, which comprises the steps of: dissolving amagnesium compound and a nonmetallocene complex in a solvent, to obtaina magnesium compound solution; introducing into the magnesium compoundsolution a precipitating agent to obtain a modified carrier; andtreating the modified carrier with a chemical treating agent selectedfrom the group consisting of Group IVB metal compounds to obtain thesupported nonmetallocene catalyst.

More specifically, this invention relates to the following aspects.

1. A process for producing a supported nonmetallocene catalyst,comprising the steps of: dissolving a magnesium compound and anonmetallocene complex in a solvent, to obtain a magnesium compoundsolution; and drying the magnesium compound solution, or introducinginto the magnesium compound solution a precipitating agent, to obtainthe supported nonmetallocene catalyst.

2. A process for producing a supported nonmetallocene catalyst,comprising the steps of: dissolving a magnesium compound and anonmetallocene complex in a solvent, to obtain a magnesium compoundsolution; drying the magnesium compound solution, or introducing intothe magnesium compound solution a precipitating agent, to obtain amodified carrier; and treating the modified carrier with a chemicaltreating agent selected from the group consisting of a Group IVB metalcompound to obtain the supported nonmetallocene catalyst.

3. The process according to any of the aforesaid aspects, furthercomprising the step of pre-treating the modified carrier with anassistant chemical treating agent selected from the group consisting ofan aluminoxane, an alkylaluminum and any combination thereof beforetreating the modified carrier with the chemical treating agent.

4. The process according to any of the aforesaid aspects, wherein themagnesium compound is one or more selected from the group consisting ofa magnesium halide, an alkoxy magnesium halide, an alkoxy magnesium, analkyl magnesium, an alkyl magnesium halide and an alkyl alkoxymagnesium, preferably one or more selected from the group consisting ofa magnesium halide, more preferably magnesium chloride.

5. The process according to any of the aforesaid aspects, wherein thesolvent is one or more selected from the group consisting of a C₆₋₁₂aromatic hydrocarbon, a halogenated C₆₋₁₂ aromatic hydrocarbon, an esterand an ether, preferably one or more selected from the group consistingof a C₆₋₁₂ aromatic hydrocarbon and tetrahydrofuran, more preferablytetrahydrofuran.

6. The process according to any of the aforesaid aspects, wherein thenonmetallocene complex is one or more selected from the group consistingof the compounds having the following structure,

preferably one or more selected from the group consisting of thefollowing compound (A) and the following compound (B),

more preferably one or more selected from the group consisting of thefollowing compound (A-1), the following compound (A-2), the followingcompound (A-3), the following compound (A-4), the following compound(B-1), the following compound (B-2), the following compound (B-3), andthe following compound (B-4),

in all of the aforesaid formulae,

q is 0 or 1;

d is 0 or 1;

m is 1, 2 or 3;

M is selected from the group consisting of a Group III to XI metal atomin the Periodic Table of Elements, preferably from the group consistingof a Group IVB metal atom, more preferably from the group consisting ofTi(IV) and Zr(IV);

n is 1, 2, 3 or 4, depending on the valence of the central metal atom M;

X is selected from the group consisting of a halogen atom, a hydrogenatom, a C₁-C₃₀ hydrocarbyl, a substituted C₁-C₃₀ hydrocarbyl, anoxygen-containing group, a nitrogen-containing group, asulfur-containing group, a boron-containing group, analuminium-containing group, a phosphor-containing group, asilicon-containing group, a germanium-containing group, and atin-containing group, when multiple Xs exist, the Xs may be the same asor different from one another, and may form a bond or a ring with oneanother;

A is selected from the group consisting of an oxygen atom, a sulfuratom, a selenium atom,

—NR²³R²⁴, —N(O)R²⁵R²⁶,

—PR²⁸R²⁹, —P(O)R³⁰OR³¹, a sulfone group, a sulfoxide group and—Se(O)R³⁹, wherein N, O, S, Se and P each represents a coordinationatom;

B is selected from the group consisting of a nitrogen atom, anitrogen-containing group, a phosphor-containing group and a C₁-C₃₀hydrocarbyl;

D is selected from the group consisting of a nitrogen atom, an oxygenatom, a sulfur atom, a selenium atom, a phosphor atom, anitrogen-containing group, a phosphor-containing group, a C₁-C₃₀hydrocarbyl, a sulfone group, a sulfoxide group,

—N(O)R²⁵R²⁶,

and —P(O)R³²(OR³³), wherein N, O, S, Se and P each represents acoordination atom;

E is selected from the group consisting of a nitrogen-containing group,an oxygen-containing group, a sulfur-containing group, aselenium-containing group, a phosphor-containing group and a cyanogroup, wherein N, O, S, Se and P each represents a coordination atom;

F is selected from the group consisting of a nitrogen atom, anitrogen-containing group, an oxygen-containing group, asulfur-containing group, a selenium-containing group and aphosphor-containing group, wherein N, O, S, Se and P each represents acoordination atom;

G is selected from the group consisting of a C₁-C₃₀ hydrocarbyl, asubstituted C₁-C₃₀ hydrocarbyl and an inert functional group;

Y is selected from the group consisting of an oxygen atom, anitrogen-containing group, an oxygen-containing group, asulfur-containing group, a selenium-containing group and aphosphor-containing group, wherein N, O, S, Se and P each represents acoordination atom;

Z is selected from the group consisting of a nitrogen-containing group,an oxygen-containing group, a sulfur-containing group, aselenium-containing group, a phosphor-containing group and a cyanogroup, wherein N, O, S, Se and P each represents a coordination atom;

→ represents a single bond or a double bond;

— represents a covalent bond or an ionic bond;

- - - represents a coordination bond, a covalent bond or an ionic bond;

R¹ to R⁴, R⁶ to R³⁶, R³⁸ and R³⁹ are each independently selected fromthe group consisting of a hydrogen atom, a C₁-C₃₀ hydrocarbyl, asubstituted C₁-C₃₀ hydrocarbyl and an inert functional group, whereinthese groups may be identical to or different from one another, and anyadjacent groups may form a bond or a ring (preferably an aromatic ring)with one another; and

R⁵ is selected from the group consisting of the lone pair electron onthe nitrogen atom, a hydrogen atom, a C₁-C₃₀ hydrocarbyl, a substitutedC₁-C₃₀ hydrocarbyl, an oxygen-containing group, a sulfur-containinggroup, a nitrogen-containing group, a selenium-containing group, and aphosphor-containing group, with the proviso that when R⁵ is theoxygen-containing group, the sulfur-containing group, thenitrogen-containing group, the selenium-containing group or thephosphor-containing group, N, O, S, P and Se in the group R⁵ each canact as a coordination atom to coordinate with the central metal atom(the Group IVB metal atom),

more preferably one or more selected from the group consisting of thefollowing compounds,

more preferably one or more selected from the group consisting of thefollowing compounds,

7. The process according to any of the aforesaid aspects, wherein, thehalogen atom is selected from the group consisting of F, Cl, Br and I,the nitrogen-containing group is selected from the group consisting of

—NR²³R²⁴, -T-NR²³R²⁴ and —N(O)R²⁵R²⁶,

the phosphor-containing group is selected from the group consisting of

—PR²⁸R²⁹, —P(O)R³⁰R³¹ and —P(O)R³²(OR³³),

the oxygen-containing group is selected from the group consisting ofhydroxy, —OR⁴ and -T-OR³⁴,

the sulfur-containing group is selected from the group consisting of—SR³⁵, -T-SR³⁵, —S(O)R³⁶ and -T-SO₂R³⁷,

the selenium-containing group is selected from the group consisting of—SeR³⁸, -T-SeR³⁸, —Se(O)R³⁹ and -T-Se(O)R³⁹,

the group T is selected from the group consisting of a C₁-C₃₀hydrocarbyl, a substituted C₁-C₃₀ hydrocarbyl and an inert functionalgroup,

R³⁷ is selected from the group consisting of a hydrogen atom, a C₁-C₃₀hydrocarbyl, a substituted C₁-C₃₀ hydrocarbyl and an inert functionalgroup,

the C₁-C₃₀ hydrocarbyl is selected from the group consisting of a C₁-C₃₀alkyl group, a C₇-C₅₀ alkylaryl group, a C₇-C₅₀ aralkyl group, a C₃-C₃₀cyclic alkyl group, a C₂-C₃₀ alkenyl group, a C₂-C₃₀ alkynyl group, aC₅-C₃₀ aryl group, a C₈-C₃₀ fused-ring group and a C₄-C₃₀ heterocyclegroup, wherein the heterocycle group contains 1 to 3 hetero atom(s)selected from the group consisting of a nitrogen atom, an oxygen atomand a sulfur atom,

the substituted C₁-C₃₀ hydrocarbyl is selected from the group consistingof the C₁-C₃₀ hydrocarbyl having one or more substituent(s) selectedfrom the halogen atom and the C₁-C₃₀ alkyl group,

the inert functional group is selected from the group consisting of thehalogen atom, the oxygen-containing group, the nitrogen-containinggroup, a silicon-containing group, a germanium-containing group, thesulfur-containing group, a tin-containing group, a C₁-C₁₀ ester groupand a nitro group, the boron-containing group is selected from the groupconsisting of BF₄ ⁻, (C₆F₅)₄B⁻ and (R⁴⁰BAr₃)⁻,

the aluminium-containing group is selected from the group consisting ofan alkyl aluminium, AlPh₄ ⁻, AlF₄ ⁻, AlCl₄ ⁻, AlBr₄ ⁻, AlI₄ ⁻ andR⁴AlAr₃ ⁻,

the silicon-containing group is selected from the group consisting of—SiR⁴²R⁴³R⁴⁴, and -T-SiR⁴⁵,

the germanium-containing group is selected from the group consisting of—GeR⁴⁶R⁴⁷R⁴⁸, and -T-GeR⁴⁹,

the tin-containing group is selected from the group consisting of—SnR⁵⁰R⁵¹R⁵²-T-SnR⁵³ and -T-Sn(O)R⁵⁴,

the Ar group represents a C₆-C₃₀ aryl group,

R⁴⁰ to R⁵⁴ are each independently selected from the group consisting ofa hydrogen atom, the C₁-C₃₀ hydrocarbyl, the substituted C₁-C₃₀hydrocarbyl and the inert functional group, wherein these groups may beidentical to or different from one another, and any adjacent groups mayform a bond or a ring with one another, and

the group T is defined as aforesaid.

8. The process according to any of the aforesaid aspects, wherein ratioby molar of the magnesium compound (based on Mg) to the nonmetallocenecomplex is 1:0.01-1, preferably 1:0.04-0.4, more preferably 1:0.08-0.2,ratio of the magnesium compound to the solvent is 1 mol:75˜400 ml,preferably 1 mol:150˜300 ml, more preferably 1 mol:200˜250 ml, and ratioby volume of the precipitating agent to the solvent is 1:0.2˜5,preferably 1:0.5˜2, more preferably 1:0.8˜1.5.

9. The process according to any of the aforesaid aspects, wherein theprecipitating agent is one or more selected from the group consisting ofan alkane, a cyclic alkane, a halogenated alkane and a halogenatedcyclic alkane, preferably one or more selected from the group consistingof pentane, hexane, heptane, octane, nonane, decane, cyclohexane,cyclopentane, cycloheptane, cyclodecane, cyclononane, dichloromethane,dichloro hexane, dichloro heptane, trichloro methane, trichloro ethane,trichloro butane, dibromo methane, dibromo ethane, dibromo heptane,tribromo methane, tribromo ethane, tribromo butane, chlorinatedcyclopentane, chlorinated cyclohexane, chlorinated cycloheptane,chlorinated cyclooctane, chlorinated cyclononane, chlorinatedcyclodecane, brominated cyclopentane, brominated cyclohexane, brominatedcycloheptane, brominated cyclooctane, brominated cyclononane andbrominated cyclodecane, more preferably one or more selected from thegroup consisting of hexane, heptane, decane and cyclohexane, mostpreferably hexane.

10. The process according to any of the aforesaid aspects, wherein ratioby molar of the magnesium compound (based on Mg) to the nonmetallocenecomplex is 1:0.01-1, preferably 1:0.04-0.4, more preferably 1:0.08-0.2,ratio of the magnesium compound to the solvent is 1 mol:75˜400 ml,preferably 1 mol:150˜300 ml, more preferably 1 mol:200˜250 ml, ratio byvolume of the precipitating agent to the solvent is 1:0.2˜5, preferably1:0.5˜2, more preferably 1:0.8˜1.5, and ratio by molar of the magnesiumcompound (based on Mg) to the chemical treating agent (based on theGroup IVB metal) is 1:0.01-1, preferably 1:0.01-0.50, more preferably1:0.10-0.30.

11. The process according to any of the aforesaid aspects, wherein theGroup IVB metal compound is one or more selected from the groupconsisting of a Group IVB metal halide, a Group IVB metal alkylate, aGroup IVB metal alkoxylate, a Group IVB metal alkyl halide, and a GroupIVB metal alkoxy halide, preferably one or more selected from the groupconsisting of a Group IVB metal halide, more preferably one or moreselected from the group consisting of TiCl₄, TiBr₄, ZrCl₄, ZrBr₄, HfCl₄and HfBr₄, more preferably one or more selected from the groupconsisting of TiCl₄ and ZrCl₄.

12. The process according to any of the aforesaid aspects, wherein thealuminoxane is one or more selected from the group consisting of methylaluminoxane, ethyl aluminoxane, isobutyl aluminoxane and n-butylaluminoxane, preferably one or more selected from the group consistingof methyl aluminoxane and isobutyl aluminoxane, and the alkylaluminum isone or more selected from the group consisting of trimethyl aluminum,triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, tri-n-butylaluminum, triisoamyl aluminum, tri-n-amyl aluminum, trihexyl aluminum,tri-iso-hexyl aluminum, diethyl methyl aluminum and ethyl dimethylaluminum, more preferably one or more selected from the group consistingof trimethyl aluminum, triethyl aluminum, tripropyl aluminum andtriisobutyl aluminum, most preferably one or more selected from thegroup consisting of triethyl aluminum and triisobutyl aluminum.

13. The process according to any of the aforesaid aspects, wherein ratioby molar of the magnesium compound (based on Mg) to the assistantchemical treating agent (based on Al) is 1:0-1.0, preferably 1:0-0.5,more preferably 1:0.1-0.5.

14. A supported nonmetallocene catalyst, produced in line with theprocess according to any of the aspects 1 to 13.

15. An olefin homopolymerization/copolymerization process, wherein thesupported nonmetallocene catalyst according to the aspect 14 is used asthe main catalyst, in combination of one or more selected from the groupconsisting of an aluminoxane, an alkylaluminum, a halogenated alkylaluminum, a fluoroborane, an alkylboron and an alkylboron ammonium saltas the co-catalyst, for homopolymerization or copolymerization of theolefin.

16. An olefin homopolymerization/copolymerization process, comprisingthe steps of: producing a supported nonmetallocene catalyst in line withthe process according to any of the aspects 1 to 13; and using thesupported nonmetallocene catalyst as the main catalyst, in combinationof one or more selected from the group consisting of an aluminoxane, analkylaluminum, a halogenated alkyl aluminum, a fluoroborane, analkylboron and an alkylboron ammonium salt as the co-catalyst, forhomopolymerization or copolymerization of the olefin.

Effect of the Invention

According to the first and second embodiments of this invention, thefollowing effects can be obtained.

The process for producing the supported nonmetallocene catalystaccording to this invention is simple and feasible. It is easy to adjustthe load of the nonmetallocene complex, and it is possible for it toperform sufficiently in catalyzing olefin polymerization to obtain anolefin polymer product.

According to the process of this invention (concerning the firstembodiment), the catalyst has been produced by directly drying themagnesium compound solution, and therefore it is easy to adjust thecomposition and amount of the essential materials in the catalyst. Andthe activity of the resultant catalyst is higher than that obtained byfiltering, washing and drying the magnesium compound solution.

According to the process of this invention (concerning the secondembodiment), the catalyst has been produced by sufficientlyprecipitating the magnesium compound solution in the presence of aprecipitating agent and then filtering, washing and drying theresultant, and therefore the bonding between the essential materials inthe catalyst is relatively strong.

When a catalyst system is constituted by using the supported single sitenonmetallocene catalyst produced by the present process in combinationwith a co-catalyst, the polymer resulted from olefin polymerizationexhibits a narrowed molecular weight distribution, when used forcopolymerization, the catalyst system shows a significant co-monomereffect, i.e. under relatively the same conditions, the activity incopolymerization is higher than that in homopolymerization.

According to the third and fourth embodiments of this invention, thefollowing effects can be obtained.

The process for producing the supported nonmetallocene catalystaccording to this invention is simple and feasible, and it is easy tocontrol the composition and amount of the essential materials in thecatalyst. Further, it is easy to adjust the load of the nonmetallocenecomplex, and it is possible for it to perform sufficiently in catalyzingolefin polymerization to obtain an olefin polymer product. Stillfurther, it is possible to adjust the molecular weight distribution ofthe polymer and the viscosity averaged molecular weight of the ultrahigh molecular weight polyethylene by altering the amount of thenonmetallocene complex to be introduced.

Further, by altering the amount of the assistant chemical treating agentand that of the chemical treating agent to be introduced, it is possibleto obtain a supported nonmetallocene catalyst showing a easilycontrollable polymerization activity, from low to high, wherebyresponding to different olefin polymerization requirements, and it ispossible to adjust the performances of the catalyst and the propertiesof the polymer in combination of the step of altering the amount of thenonmetallocene complex to be introduced.

The active components (i.e. the nonmetallocene complex and the chemicaltreating agent) in the supported nonmetallocene catalyst produced inline with the process according to this invention show a synergiceffect, i.e. the activity obtained with the case when both componentsexist is higher than that when only either component exists.

According to the process of this invention (concerning the thirdembodiment), the modified carrier has been produced by directly dryingthe magnesium compound solution, and therefore it is easy to adjust thecomposition and amount of the essential materials in the catalyst. Andthe activity of the resultant catalyst is higher than that obtained byfiltering, washing and drying the magnesium compound solution.

Further discovered is that, when a catalyst system is constituted byusing the catalyst according to this invention in combination with aco-catalyst, only a comparatively small amount of the co-catalyst (forexample, methyl aluminoxane or triethyl aluminium) is needed to achievea comparatively high polymerization activity, and when used forcopolymerization, the catalyst system shows a significant co-monomereffect, i.e. under relatively the same conditions, the activity incopolymerization is higher than that in homopolymerization. Further, thepolymer (for example polyethylene) resulted from olefinhomopolymerization or copolymerization has a desirable polymermorphology and a high polymer bulk density.

DETAILED DESCRIPTION OF THE INVENTION

This invention will be described in details hereinafter with referenceto the following specific embodiments. However, it is known that theprotection scope of this invention should not be construed as limited tothese specific embodiments, but rather determined by the attachedclaims.

According to this invention, generally disclosed are the following firstto fourth embodiments.

The first embodiment relates to a process for producing a supportednonmetallocene catalyst, which comprises the steps of: dissolving amagnesium compound and a nonmetallocene complex in a solvent, to obtaina magnesium compound solution; and drying the magnesium compoundsolution to obtain the supported nonmetallocene catalyst.

The second embodiment relates to a process for producing a supportednonmetallocene catalyst, which comprises the steps of: dissolving amagnesium compound and a nonmetallocene complex in a solvent, to obtaina magnesium compound solution; and introducing into the magnesiumcompound solution a precipitating agent to obtain the supportednonmetallocene catalyst.

The third embodiment relates to a process for producing a supportednonmetallocene catalyst, which comprises the steps of: dissolving amagnesium compound and a nonmetallocene complex in a solvent, to obtaina magnesium compound solution; drying the magnesium compound solution toobtain a modified carrier; and treating the modified carrier with achemical treating agent selected from the group consisting of Group IVBmetal compounds to obtain the supported nonmetallocene catalyst.

The fourth embodiment relates to a process for producing a supportednonmetallocene catalyst, which comprises the steps of: dissolving amagnesium compound and a nonmetallocene complex in a solvent, to obtaina magnesium compound solution; introducing into the magnesium compoundsolution a precipitating agent to obtain a modified carrier; andtreating the modified carrier with a chemical treating agent selectedfrom the group consisting of Group IVB metal compounds to obtain thesupported nonmetallocene catalyst.

First of all, the step of obtaining the magnesium compound solutionaccording to the first to fourth embodiments of this invention isdetailedly described as follows.

Specifically, the magnesium compound (solid) and the nonmetallocenecomplex are dissolved in a suitable solvent (hereinafter referred to asa solvent for dissolving the magnesium compound) to obtain the magnesiumcompound solution.

As the solvent, a C₆₋₁₂ aromatic hydrocarbon, a halogenated C₆₋₁₂aromatic hydrocarbon, an ester and an ether can be exemplified.Specifically, toluene, xylene, trimethyl benzene, ethyl benzene, diethylbenzene, chlorinated toluene, chlorinated ethyl benzene, brominatedtoluene, brominated ethyl benzene, ethyl acetate and tetrahydrofuran canbe exemplified. Preference is given to the C₆₋₁₂ aromatic hydrocarbon ortetrahydrofuran, more preferably tetrahydrofuran.

The solvents could be used with one kind or as a mixture of two or morekinds at any ratio therebetween.

For preparation of the magnesium compound solution, the magnesiumcompound and the nonmetallocene complex are metered into and dissolvedin said solvent.

During preparation of the magnesium compound solution, it is desirablethat the ratio of the magnesium compound (based on Mg and on a solidbasis) to the solvent for dissolving the magnesium compound is generally1 mol:75˜400 ml, preferably 1 mol:150˜300 ml, more preferably 1mol:200˜250 ml.

According to this invention, as the amount of the nonmetallocene complexto be used, it is desirable that the ratio by molar of the magnesiumcompound (based on Mg and on a solid basis) to the nonmetallocenecomplex is 1:0.01-1, preferably 1:0.04-0.4, more preferably 1:0.08-0.2.

The duration for preparing the magnesium compound solution (i.e. theduration for dissolving the magnesium compound and the nonmetallocenecomplex) is not specifically limited, usually 0.5 to 24 hours,preferably 4 to 24 hours. During preparation of the magnesium compoundsolution, any stirring means for example, a stirring paddle (whoserotational speed could be 10 to 1000 r/min), could be used to facilitatedissolution of the magnesium compound and the nonmetallocene complex. Ifneeded, heat can be suitably applied to facilitate the dissolution.

The magnesium compound is further described as follows.

According to this invention, the term “magnesium compound” is explainedin a normal sense as known in this field, and refers to an organic orinorganic solid anhydrous Mg-containing compound conventionally used asa carrier for a supported catalyst for olefin polymerization.

According to this invention, as the magnesium compound, a magnesiumhalide, an alkoxy magnesium halide, an alkoxy magnesium, an alkylmagnesium, an alkyl magnesium halide and an alkyl alkoxy magnesium canbe exemplified.

Specifically, the magnesium halide for example, could be selected fromthe group consisting of magnesium chloride (MgCl₂), magnesium bromide(MgBr₂), magnesium iodide (MgI₂) and magnesium fluoride (MgF₂), etc.,such as magnesium chloride.

The alkoxy magnesium halide for example, could be selected from thegroup consisting of methoxy magnesium chloride (Mg(OCH₃)Cl), ethoxymagnesium chloride (Mg(OC₂H₅)Cl), propoxy magnesium chloride(Mg(OC₃H₇)Cl), n-butoxy magnesium chloride (Mg(OC₄H₉)Cl), isobutoxymagnesium chloride (Mg(i-OC₄H₉)Cl), methoxy magnesium bromide(Mg(OCH₃)Br), ethoxy magnesium bromide (Mg(OC₂H₅)Br), propoxy magnesiumbromide (Mg(OC₃H₇)Br), n-butoxy magnesium bromide (Mg(OC₄H₉)Br),isobutoxy magnesium bromide (Mg(i-OC₄H₉)Br), methoxy magnesium iodide(Mg(OCH₃)I), ethoxy magnesium iodide (Mg(OC₂H₅)I), propoxy magnesiumiodide (Mg(OC₃H₇)I), n-butoxy magnesium iodide (Mg(OC₄H₉)I) andisobutoxy magnesium iodide (Mg(i-OC₄H₉)I), etc., such as methoxymagnesium chloride, ethoxy magnesium chloride and isobutoxy magnesiumchloride.

The alkoxy magnesium for example, could be selected from the groupconsisting of methoxy magnesium (Mg(OCH₃)₂), ethoxy magnesium(Mg(OC₂H₅)₂), propoxy magnesium (Mg(OC₃H₇)₂), butoxy magnesium(Mg(OC₄H₉)₂), isobutoxy magnesium (Mg(i-OC₄H₉)₂) and 2-ethyl hexyloxymagnesium (Mg(OCH₂CH(C₂H₅)C₄H)₂), etc., such as ethoxy magnesium andisobutoxy magnesium.

The alkyl magnesium for example, could be selected from the groupconsisting of methyl magnesium (Mg(CH₃)₂), ethyl magnesium (Mg(C₂H₅)₂),propyl magnesium (Mg(C₃H₇)₂), n-butyl magnesium (Mg(C₄H₉)₂) and isobutylmagnesium (Mg(i-C₄H₉)₂), etc., such as ethyl magnesium and n-butylmagnesium.

The alkyl magnesium halide for example, could be selected from the groupconsisting of methyl magnesium chloride (Mg(CH₃)Cl), ethyl magnesiumchloride (Mg(C₂H₅)Cl), propyl magnesium chloride (Mg(C₃H₇)Cl), n-butylmagnesium chloride (Mg(C₄H₉)Cl), isobutyl magnesium chloride(Mg(i-C₄H₉)Cl), methyl magnesium bromide (Mg(CH₃)Br), ethyl magnesiumbromide (Mg(C₂H₅)Br), propyl magnesium bromide (Mg(C₃H₇)Br), n-butylmagnesium bromide (Mg(C₄H₉)Br), isobutyl magnesium bromide(Mg(i-C₄H₉)Br), methyl magnesium iodide (Mg(CH₃)I), ethyl magnesiumiodide (Mg(C₂H₅)I), propyl magnesium iodide (Mg(C₃H₇)I), n-butylmagnesium iodide (Mg(C₄H₉)I) and isobutyl magnesium iodide(Mg(i-C₄H₉)I), etc., such as methyl magnesium chloride, ethyl magnesiumchloride and isobutyl magnesium chloride.

The alkyl alkoxy magnesium for example, could be selected from the groupconsisting of methyl methoxy magnesium (Mg(OCH₃)(CH₃)), methyl ethoxymagnesium (Mg(OC₂H₅)(CH₃)), methyl propoxy magnesium (Mg(OC₃H₇)(CH₃)),methyl n-butoxy magnesium (Mg(OC₄H₉)(CH₃)), methyl isobutoxy magnesium(Mg(i-OC₄H₉)(CH₃)), ethyl methoxy magnesium (Mg(OCH₃)(C₂H₅)), ethylethoxy magnesium (Mg(OC₂H₅)(C₂H₅)), ethyl propoxy magnesium(Mg(OC₃H₇)(C₂H₅)), ethyl n-butoxy magnesium (Mg(OC₄H₉)(C₂H₅)), ethylisobutoxy magnesium (Mg(i-OC₄H₉)(C₂H₅)), propyl methoxy magnesium(Mg(OCH₃)(C₃H₇)), propyl ethoxy magnesium (Mg(OC₂H₅)(C₃H₇)), propylpropoxy magnesium (Mg(OC₃H₇)(C₃H₇)), propyl n-butoxy magnesium(Mg(OC₄H₉)(C₃H₇)), propyl isobutoxy magnesium (Mg(i-OC₄H₉)(C₃H₇)),n-butyl methoxy magnesium (Mg(OCH₃)(C₄H₉)), n-butyl ethoxy magnesium(Mg(OC₂H₅)(C₄H₉)), n-butyl propoxy magnesium (Mg(OC₃H₇)(C₄H₉)), n-butyln-butoxy magnesium (Mg(OC₄H₉)(C₄H₉)), n-butyl isobutoxy magnesium(Mg(i-OC₄H₉)(C₄H₉)), isobutyl methoxy magnesium (Mg(OCH₃)(i-C₄H₉)),isobutyl ethoxy magnesium (Mg(OC₂H₅) (i-C₄H₉)), isobutyl propoxymagnesium (Mg(OC₃H₇) (i-C₄H₉)), isobutyl n-butoxy magnesium (Mg(OC₄H₉)(i-C₄H₉)) and isobutyl isobutoxy magnesium (Mg(i-OC₄H₉) (i-C₄H₉)), etc.,such as butyl ethoxy magnesium.

The magnesium compounds could be used with one kind or as a mixture oftwo or more kinds, but without any limitation thereto.

For example, if more than one magnesium compounds are used as a mixture,the ratio by molar of one magnesium compound to another magnesiumcompound in the mixture could be, for example, 0.25 to 4:1, such as 0.5to 3:1, such as 1 to 2:1.

According to this invention, the term “nonmetallocene complex” refers toan organic metallic compound capable of exhibiting a catalysis activityin olefin polymerization when combined with an aluminoxane (sometimeshereinafter referred to as a nonmetallocene complex for olefinpolymerization). The compound contains a central metal atom and at leastone multi-dentate ligand (preferably a tri or more -dentate ligand)bonding to the central metal atom by a coordination bond. The term“nonmetallocene ligand” corresponds to the multi-dentate ligand.

According to this invention, the nonmetallocene complex is selected fromthe compounds having the following structure,

According to aforesaid chemical formula, the ligands which form acoordination bond with the central metal atom M contain n of the groupsX and m of the multi-dentate ligands (the structure in the parenthesis).According to the chemical formula of said multi-dentate ligand, thegroups A, D and E (the coordination groups) form a coordination bondwith the central metal atom M through the coordination atoms (forexample, hetero atoms like N, O, S, Se and P) contained in these groups.

According to this invention, the absolute value of the total sum of thenegative charges carried by all of the ligands (including the group Xand the multi-dentate ligand) is equal to that of the positive chargescarried by the central metal atom M.

According to a further embodiment of this invention, the nonmetallocenecomplex is selected from the following compound (A) and the followingcompound (B),

According to a further embodiment of this invention, the nonmetallocenecomplex is selected from the following compound (A-1), the followingcompound (A-2), the following compound (A-3), the following compound(A-4), the following compound (B-1), the following compound (B-2), thefollowing compound (B-3), and the following compound (B-4),

In all of the aforesaid formulae,

q is 0 or 1;

d is 0 or 1;

m is 1, 2 or 3;

M is selected from the group consisting of a Group III to XI metal atomin the Periodic Table of Elements, preferably a Group IVB metal atom,for example, Ti(IV), Zr(IV), Hf(IV), Cr(III), Fe(III), Ni(II), Pd(II) orCo(II);

n is 1, 2, 3 or 4, depending on the valence of the central metal atom M;

X is selected from the group consisting of a halogen atom, a hydrogenatom, a C₁-C₃₀ hydrocarbyl, a substituted C₁-C₃₀ hydrocarbyl, anoxygen-containing group, a nitrogen-containing group, asulfur-containing group, a boron-containing group, analuminium-containing group, a phosphor-containing group, asilicon-containing group, a germanium-containing group, and atin-containing group, when multiple Xs exist, the Xs may be the same asor different from one another, and may form a bond or a ring with oneanother;

A is selected from the group consisting of an oxygen atom, a sulfuratom, a selenium atom,

—NR²³R²⁴, —N(O)R²⁵R²⁶,

—PR²⁸R²⁹, —P(O)R³⁰OR³¹, a sulfone group, a sulfoxide group and—Se(O)R³⁹, wherein N, O, S, Se and P each represents a coordinationatom;

B is selected from the group consisting of a nitrogen atom, anitrogen-containing group, a phosphor-containing group and a C₁-C₃₀hydrocarbyl;

D is selected from the group consisting of a nitrogen atom, an oxygenatom, a sulfur atom, a selenium atom, a phosphor atom, anitrogen-containing group, a phosphor-containing group, a C₁-C₃₀hydrocarbyl, a sulfone group, a sulfoxide group,

—N(O)R²⁵R²⁶,

and —P(O)R³²(OR³³), wherein N, O, S, Se and P each represents acoordination atom;

E is selected from the group consisting of a nitrogen-containing group,an oxygen-containing group, a sulfur-containing group, aselenium-containing group, a phosphor-containing group and a cyano group(—CN), wherein N, O, S, Se and P each represents a coordination atom;

F is selected from the group consisting of a nitrogen atom, anitrogen-containing group, an oxygen-containing group, asulfur-containing group, a selenium-containing group and aphosphor-containing group, wherein N, O, S, Se and P each represents acoordination atom;

G is selected from the group consisting of a C₁-C₃₀ hydrocarbyl, asubstituted C₁-C₃₀ hydrocarbyl and an inert functional group;

Y is selected from the group consisting of an oxygen atom, anitrogen-containing group, an oxygen-containing group, asulfur-containing group, a selenium-containing group and aphosphor-containing group, wherein N, O, S, Se and P each represents acoordination atom;

Z is selected from the group consisting of a nitrogen-containing group,an oxygen-containing group, a sulfur-containing group, aselenium-containing group, a phosphor-containing group and a cyano group(—CN), for example, —NR²³R²⁴, —N(O)R²⁵R²⁶, —PR²⁸R²⁹, —P(O)R³⁰R³¹, —OR³⁴,—SR³⁵, —S(O)R³⁶, —SeR³⁸ or —Se(O)R³⁹, wherein N, O, S, Se and P eachrepresents a coordination atom;

→ represents a single bond or a double bond;

— represents a covalent bond or an ionic bond;

- - - represents a coordination bond, a covalent bond or an ionic bond;

R¹ to R⁴, R⁶ to R³⁶, R³⁸ and R³⁹ are each independently selected fromthe group consisting of a hydrogen atom, a C₁-C₃₀ hydrocarbyl, asubstituted C₁-C₃₀ hydrocarbyl (preferably a halogenated hydrocarbyl,for example —CH₂Cl and —CH₂CH₂Cl) and an inert functional group, whereinthese groups may be identical to or different from one another, and anyadjacent groups (for example R¹ and R², R⁶ and R⁷, R⁷ and R⁸, R⁸ and R⁹,R¹³ and R¹⁴, R¹⁴ and R¹⁵, R¹⁵ and R¹⁶, R¹⁸ and R¹⁹, R¹⁹ and R²⁰, R²⁰ andR²¹, R²³ and R²⁴, or R²⁵ and R²⁶) may form a bond or a ring (preferablyan aromatic ring, for example a unsubstituted benzene ring or a benzenering substituted by one to four of a C₁-C₃₀ hydrocarbyl, a substitutedC₁-C₃₀ hydrocarbyl (preferably a halogenated hydrocarbyl, for example—CH₂Cl and —CH₂CH₂Cl) or an inert functional group) with one another;and

R⁵ is selected from the group consisting of the lone pair electron onthe nitrogen atom, a hydrogen atom, a C₁-C₃₀ hydrocarbyl, a substitutedC₁-C₃₀ hydrocarbyl, an oxygen-containing group, a sulfur-containinggroup, a nitrogen-containing group, a selenium-containing group, and aphosphor-containing group, with the proviso that when R⁵ is theoxygen-containing group, the sulfur-containing group, thenitrogen-containing group, the selenium-containing group or thephosphor-containing group, N, O, S, P and Se in the group R⁵ each canact as a coordination atom to coordinate with the central metal atom(the Group IVB metal atom).

According to this invention, in all of the aforesaid formulae, ifnecessary, any two or more adjacent groups (for example R²¹ and thegroup Z, or R¹³ and the group Y) may form a ring with one another,preferably a C₆-C₃₀ aromatic heteroatomic ring containing the heteroatom originated from the group Z or Y, for example a pyridine ring,wherein the aromatic heteroatomic ring is optionally substituted by oneor more substituent(s) selected from the group consisting of a C₁-C₃₀hydrocarbyl, a substituted C₁-C₃₀ hydrocarbyl and an inert functionalgroup.

In the context of this invention, the halogen atom is selected from thegroup consisting of F, Cl, Br and I the nitrogen-containing group isselected from the group consisting of

—NR²³R²⁴, -T-NR²³R²⁴ and —N(OR²⁵R²⁶, the phosphor-containing group isselected from the group consisting of

—PR²⁸R²⁹, —P(O)R³⁰R³¹ and —P(O)R³²(OR³³), the oxygen-containing group isselected from the group consisting of hydroxy, —OR³⁴ and -T-OR³⁴, thesulfur-containing group is selected from the group consisting of —SR³⁵,-T-SR³⁵, —S(O)R³⁶ and -T-SO₂R³⁷, the selenium-containing group isselected from the group consisting of —SeR³⁸, -T-SeR³⁸, —Se(O)R³⁹ and-T-Se(O)R³⁹, the group T is selected from the group consisting of aC₁-C₃₀ hydrocarbyl, a substituted C₁-C₃₀ hydrocarbyl and an inertfunctional group, and R³⁷ is selected from the group consisting of ahydrogen atom, a C₁-C₃₀ hydrocarbyl, a substituted C₁-C₃₀ hydrocarbyland an inert functional group.

In the context of this invention, the C₁-C₃₀ hydrocarbyl is selectedfrom the group consisting of a C₁-C₃₀ alkyl group (for example a C₁-C₆alkyl group, for example isobutyl group), a C₇-C₅₀ alkylaryl group (forexample tolyl, xylyl, diisobutyl phenyl), a C₇-C₅₀ aralkyl group (forexample benzyl), a C₃-C₃₀ cyclic alkyl group, a C₂-C₃₀ alkenyl group, aC₂-C₃₀ alkynyl group, a C₆-C₃₀ aryl group (for example phenyl, naphthyl,anthracyl), a C₈-C₃₀ fused-ring group and a C₄-C₃₀ heterocyclic group,wherein the heterocyclic group contains 1 to 3 hetero atom(s) selectedfrom the group consisting of a nitrogen atom, an oxygen atom and asulfur atom, including for example a pyridyl group, a pyrrolyl group, afuranyl group and a thienyl group.

In the context of this invention, depending on the nature of therelevant groups to which the C₁-C₃₀ hydrocarbyl bond, it is obvious to aperson skilled in the art that the C₁-C₃₀ hydrocarbyl may intend aC₁-C₃₀ hydrocarbon-diyl (a bivalent group, or referred to as a C₁-C₃₀hydrocarbylene group) or a C₁-C₃₀ hydrocarbon-triyl (a trivalent group).

In the context of this invention, the substituted C₁-C₃₀ hydrocarbylintends the aforesaid C₁-C₃₀ hydrocarbyl having one or more inertsubstituent(s). By inert, it means that these inert substituents willnot substantially interfere with the coordination process between theaforesaid coordination groups (i.e. the aforesaid groups A, D, E, F, Yand Z, or further, if applicable, the group R⁵) and the central metalatom M. In other words, restricted by the specific chemical structure ofthe present multi-dentate ligand, these substituents are incapable of orhave no chance (due to for example steric hindrance) to coordinate withthe central metal atom M to form a coordination bond therewith.Generally, the inert substituent refers to the aforesaid halogen atom orC₁-C₃₀ alkyl group (for example a C₁-C₆ alkyl group, for exampleisobutyl group).

In the context of this invention, the term “inert functional group” doesnot comprise the aforesaid C₁-C₃₀ hydrocarbyl or substituted C₁-C₃₀hydrocarbyl in its concept. As the inert functional group, the halogenatom, the oxygen-containing group, the nitrogen-containing group, asilicon-containing group, a germanium-containing group, thesulfur-containing group, a tin-containing group, a C₁-C₁₀ ester group ora nitro group (—NO₂) can be exemplified.

In the context of this invention, restricted by the specific structureof the present multi-dentate ligand, the inert functional group ischaracterized that:

(1) it will not interfere with the coordination process between theaforesaid group A, D, E, F, Y or Z and the central metal atom M, and

(2) its capability to form a coordination bond with the central metalatom M is inferior to the capability of the aforesaid group A, D, E, F,Y or Z to form a coordination bond with the central metal atom M, and itwill not displace the formed coordination between the central metal atomM and these groups.

In the context of this invention, the boron-containing group is selectedfrom the group consisting of BF₄ ⁻, (C₆F₅)₄B⁻ and (R⁴⁰BAr₃)⁻, thealuminium-containing group is selected from the group consisting of analkyl aluminium, AlPh₄ ⁻, AlF₄ ⁻, AlCl₄ ⁻, AlBr₄ ⁻, AlI₄ and R⁴¹AlAr₃ ⁻,the silicon-containing group is selected from the group consisting of—SiR⁴²R⁴³R⁴⁴, and -T-SiR⁴⁵, the germanium-containing group is selectedfrom the group consisting of —GeR⁴⁶R⁴⁷R⁴⁸, and -T-GeR⁴, thetin-containing group is selected from the group consisting of—SnR⁵⁰R⁵¹R⁵², -T-SnR⁵³ and -T-Sn(O)R⁵⁴, the Ar group represents a C₆-C₃₀aryl group, R⁴⁰ to R⁵⁴ are each independently selected from the groupconsisting of a hydrogen atom, the C₁-C₃₀ hydrocarbyl, the substitutedC₁-C₃₀ hydrocarbyl and the inert functional group, wherein these groupsmay be identical to or different from one another, and any adjacentgroups may form a bond or a ring with one another, and the group T isdefined as aforesaid.

As the nonmetallocene complex, the following compounds can be furtherexemplified.

As the nonmetallocene complex, the following compounds can be furtherexemplified.

As the nonmetallocene complex, the following compounds can be furtherexemplified.

As the nonmetallocene complex, the following compounds can be furtherexemplified.

The nonmetallocene complexes could be used with one kind or as a mixtureof two or more kinds at any ratio therebetween.

According to this invention, the multi-dentate ligand in thenonmetallocene complex does not correspond to or comprise the di-ethercompound conventionally used in this field as an electron donorcompound.

According to this invention, the multi-dentate ligand or thenonmetallocene complex can be produced in line with any process known inthis field by a person skilled in the art. For the details of theprocess, one can refer to for example WO03/010207 or the Chinese PatentNos. ZL01126323.7 and ZL02110844.7. All the references cited herein areincorporated by reference in their entireties.

According to the first embodiment of this invention, by directly dryingthe magnesium compound solution, a freely flowable solid product can beobtained, which corresponds to the supported nonmetallocene catalyst ofthis invention.

According to the first embodiment of this invention, in order todirectly dry the magnesium compound solution, any conventional process,for example, drying under an inert gas atmosphere, vacuum drying orvacuum drying under heat, can be used, preferably vacuum drying underheat. The drying is generally conducted at a temperature 5 to 15° C.lower than the boiling point of any solvent in the magnesium compoundsolution, which would be a temperature of 30 to 160° C. or 60 to 130°C., while the duration for the drying is generally, not limiting to, 2to 24 hours.

Further, according to the second embodiment of this invention, bymetering into the magnesium compound solution a precipitating agent,solid matter (solid product) is precipitated out of the magnesiumcompound solution, whereby obtaining the supported nonmetallocenecatalyst of this invention.

Or, according to the fourth embodiment of this invention, by meteringinto the magnesium compound solution a precipitating agent, solid matter(solid product) is precipitated out of the magnesium compound solution,whereby obtaining the modified carrier.

The precipitating agent is further described as follows.

According to this invention, the term “precipitating agent” is explainedin a normal sense as known in this field, and refers to a chemicallyinert liquid capable of lowering the solubility of a solute (for examplethe magnesium compound) in its solution to the degree that said soluteprecipitates from the solution as solid matter.

According to this invention, as the precipitating agent, a solvent thatrepresents as a poor solvent for the magnesium compound while as a goodsolvent for the solvent for dissolving the magnesium compound can beexemplified. For example, an alkane, a cyclic alkane, a halogenatedalkane and a halogenated cyclic alkane can be further exemplified.

As the alkane, exemplified is pentane, hexane, heptane, octane, nonaneand decane, and the like, such as hexane, heptane and decane, such ashexane.

As the cyclic alkane, exemplified is cyclohexane, cyclo pentane, cycloheptane, cyclo decane, cyclo nonane, and the like, such as cyclo hexane.

As the halogenated alkane, exemplified is dichloro methane, dichlorohexane, dichloro heptane, trichloro methane, trichloro ethane, trichlorobutane, dibromo methane, dibromo ethane, dibromo heptane, tribromomethane, tribromo ethane, tribromo butane, and the like.

As the halogenated cyclic alkane, exemplified is chlorinated cyclopentane, chlorinated cyclo hexane, chlorinated cyclo heptane,chlorinated cyclo octane, chlorinated cyclo nonane, chlorinated cyclodecane, brominated cyclo pentane, brominated cyclo hexane, brominatedcyclo heptane, brominated cyclo octane, brominated cyclo nonane,brominated cyclo decane, and the like.

The precipitating agent can be used with one kind or as a mixture of twoor more kinds at any ratio therebetween.

The precipitating agent could be added all at once or dropwise, such asall at once. During the precipitation, any stirring means could be usedto facilitate uniform dispersion of the precipitating agent throughoutthe magnesium compound solution, and eventually facilitate precipitationof the solid product. The stirring means could be in any form, forexample, as a stirring paddle, whose rotational speed could be 10 to1000 r/min.

There is no limitation as to the amount of the precipitating agent to beused, generally, the ratio by volume of the precipitating agent to thesolvent for dissolving the magnesium compound is 1:0.2˜5, preferably1:0.5˜2, more preferably 1:0.8˜1.5.

There is no limitation as to the temperature at which the precipitatingagent is, such as the normal temperature. Further, the precipitationprocess can be generally conducted at the normal temperature as well.

After completely precipitated, the thus obtained solid product isfiltered, washed and dried. There is no limitation to the process forfiltering, washing or drying, and any conventional processconventionally used in this field can be used as needed.

If needed, the washing can be generally conducted for 1 to 6 times,preferable 2 to 3 times. Herein, the solvent for washing can be the sameas or different from the precipitating agent.

The drying can be conducted in line with a conventional process, forexample, drying under an inert gas atmosphere, vacuum drying or vacuumdrying under heat, preferably drying under an inert gas atmosphere orvacuum drying under heat, most preferably vacuum drying under heat.

The drying is generally conducted at a temperature ranging from thenormal temperature to 100° C. for a duration by which the mass in dryingwill not loss weight any further. For example, in the case whereintetrahydrofuran is used as the solvent for dissolving the magnesiumcompound, the drying is generally conducted at about 80° C. under vacuumfor a duration of 2 to 12 hours, while toluene is used as the solventfor dissolving the magnesium compound, the drying is generally conductedat about 100° C. under vacuum for a duration of 4 to 24 hours.

Further, according to the third embodiment of this invention, bydirectly drying the magnesium compound solution, a freely flowable solidproduct can be obtained, which corresponds to the modified carrier ofthis invention.

In order to directly dry the magnesium compound solution, anyconventional process, for example, drying under an inert gas atmosphere,vacuum drying or vacuum drying under heat, can be used, preferablyvacuum drying under heat. The drying is generally conducted at atemperature 5 to 15° C. lower than the boiling point of any solvent inthe magnesium compound solution, which would be a temperature of 30 to160° C. or 60 to 130° C., while the duration for the drying isgenerally, not limiting to, 2 to 24 hours.

Then, according to the third and fourth embodiments of this invention,the modified carrier is treated with a chemical treating agent selectedfrom the group consisting of Group IVB metal compounds (referred to asthe chemical treating step hereinafter) so as to obtain the supportednonmetallocene catalyst of this invention.

The chemical treating agent is further described as follows.

According to this invention, a Group IVB metal compound is used as thechemical treating agent.

As the Group IVB metal compound, exemplified is a Group IVB metalhalide, a Group IVB metal alkylate, a Group IVB metal alkoxylate, aGroup IVB metal alkyl halide, and a Group IVB metal alkoxy halide.

As the Group IVB metal halide, the Group IVB metal alkylate, the GroupIVB metal alkoxylate, the Group IVB metal alkyl halide and the Group IVBmetal alkoxy halide, exemplified is a compound having the followinggeneral formula (IV).

M(OR¹)_(m)X_(n)R² _(4-m-n)  (IV)

wherein,

m is 0, 1, 2, 3, or 4,

n is 0, 1, 2, 3, or 4,

M is a Group IVB metal in the Periodic Table of Elements, for example,titanium, zirconium, hafnium and the like,

X is a halogen atom, for example, F, Cl, Br, and I, and

R¹ and R² each independently is selected from the group consisting of aC₁-C₁₀ alkyl, for example, methyl, ethyl, propyl, n-butyl, isobutyl andthe like, R¹ and R² could be identical to or different from each other.

Specifically, the Group IVB metal halide could be exemplified as forexample, titanium tetrafluoride (TiF₄), titanium tetrachloride (TiCl₄),titanium tetrabromide (TiBr₄), titanium tetraiodide (TiI₄), zirconiumtetrafluoride (ZrF₄), zirconium tetrachloride (ZrCl₄), zirconiumtetrabromide (ZrBr₄), zirconium tetraiodide (ZrI₄), hafniumtetrafluoride (HfF₄), hafnium tetrachloride (HfCl₄), hafniumtetrabromide (HfBr₄), hafnium tetraiodide (Hfl₄).

As the Group IVB metal alkylate, exemplified is tetramethyl titanium(Ti(CH₃)₄), tetraethyl titanium (Ti(CH₃CH₂)₄), tetraisobutyl titanium(Ti(i-C₄H₉)₄), tetran-butyl titanium (Ti(C₄H₉)₄), triethyl methyltitanium (Ti(CH₃)(CH₃CH₂)₃), diethyl dimethyl titanium(Ti(CH₃)₂(CH₃CH₂)₂), trimethyl ethyl titanium (Ti(CH₃)₃(CH₃CH₂)),triisobutyl methyl titanium (Ti(CH₃)(i-C₄H₉)₃), diisobutyl dimethyltitanium (Ti(CH₃)₂(i-C₄H₉)₂), trimethyl isobutyl titanium(Ti(CH₃)₃(i-C₄H₉)), triisobutyl ethyl titanium (Ti(CH₃CH₂)(i-C₄H₉)₃),diisobutyl diethyl titanium (Ti(CH₃CH₂)₂(i-C₄H₉)₂), triethyl isobutyltitanium (Ti(CH₃CH₂)₃(i-C₄H₉)), trin-butyl methyl titanium(Ti(CH₃)(C₄H₉)₃), din-butyl dimethyl titanium (Ti(CH₃)₂(C₄H₉)₂),trimethyl n-butyl titanium (Ti(CH₃)₃(C₄H₉)), trin-butyl methyl titanium(Ti(CH₃CH₂)(C₄H₉)₃), din-butyl diethyl titanium (Ti(CH₃CH₂)₂(C₄H₉)₂),triethyl n-butyl titanium (Ti(CH₃CH₂)₃(C₄H₉)), and so on, tetramethylzirconium (Zr(CH₃)₄), tetraethyl zirconium (Zr(CH₃CH₂)₄),

tetraisobutyl zirconium (Zr(i-C₄H₉)₄), tetran-butyl zirconium(Zr(C₄H₉)₄), triethyl methyl zirconium (Zr(CH₃)(CH₃CH₂)₃), diethyldimethyl zirconium (Zr(CH₃)₂(CH₃CH₂)₂), trimethyl ethyl zirconium(Zr(CH₃)₃(CH₃CH₂)), triisobutyl methyl zirconium (Zr(CH₃)(i-C₄H₉)₃),diisobutyl dimethyl zirconium (Zr(CH₃)₂(i-C₄H₉)₂), trimethyl isobutylzirconium (Zr(CH₃)₃(i-C₄H₉)), triisobutyl ethyl zirconium(Zr(CH₃CH₂)(i-C₄H₉)₃), diisobutyl diethyl zirconium(Zr(CH₃CH₂)₂(i-C₄H₉)₂), triethyl isobutyl zirconium(Zr(CH₃CH₂)₃(i-C₄H₉)), trin-butyl methyl zirconium

(Zr(CH₃)(C₄H₉)₃), din-butyl dimethyl zirconium (Zr(CH₃)₂(C₄H₉)₂),trimethyl n-butyl zirconium (Zr(CH₃)₃(C₄H₉)), trin-butyl methylzirconium (Zr(CH₃CH₂)(C₄H₉)₃), din-butyl diethyl zirconium(Zr(CH₃CH₂)₂(C₄H₉)₂), triethyl n-butyl zirconium (Zr(CH₃CH₂)₃(C₄H₉)),and so on,

tetramethyl hafnium (Hf(CH₃)₄), tetraethyl hafnium (Hf(CH₃CH₂)₄),tetraisobutyl hafnium (Hf(i-C₄H₉)₄), tetran-butyl hafnium (Hf(C₄H₉)₄),triethyl methyl hafnium (Hf(CH₃)(CH₃CH₂)₃), diethyl dimethyl hafnium(Hf(CH₃)₂(CH₃CH₂)₂), trimethyl ethyl hafnium (Hf(CH₃)₃(CH₃CH₂)),triisobutyl methyl hafnium (Hf(CH₃)(i-C₄H₉)₃), diisobutyl dimethylhafnium (Hf(CH₃)₂(i-C₄H₉)₂), trimethyl isobutyl hafnium(Hf(CH₃)₃(i-C₄H₉)), triisobutyl ethyl hafnium (Hf(CH₃CH₂)(i-C₄H₉)₃),diisobutyl diethyl hafnium (Hf(CH₃CH₂)₂(i-C₄H₉)₂), triethyl isobutylhafnium (Hf(CH₃CH₂)₃(i-C₄H₉)), trin-butyl methyl hafnium(Hf(CH₃)(C₄H₉)₃), din-butyl dimethyl hafnium (Hf(CH₃)₂(C₄H₉)₂),trimethyl n-butyl hafnium (Hf(CH₃)₃(C₄H₉)), trin-butyl methyl hafnium(Hf(CH₃CH₂)(C₄H₉)₃), din-butyl diethyl hafnium (Hf(CH₃CH₂)₂(C₄H₉)₂),triethyl n-butyl hafnium (Hf(CH₃CH₂)₃(C₄H₉)), and so on.

As the Group IVB metal alkoxylate, exemplified is tetramethoxy titanium(Ti(OCH₃)₄), tetraethoxy titanium (Ti(OCH₃CH₂)₄), tetraisobutoxytitanium (Ti(i-OC₄H₉)₄), tetran-butoxy titanium (Ti(OC₄H₉)₄), triethoxymethoxy titanium (Ti(OCH₃)(OCH₃CH₂)₃), diethoxy dimethoxy titanium(Ti(OCH₃)₂(OCH₃CH₂)₂), trimethoxy ethoxy titanium (Ti(OCH₃)₃(OCH₃CH₂)),triisobutoxy methoxy titanium (Ti(OCH₃)(i-OC₄H₉)₃), diisobutoxydimethoxy titanium (Ti(OCH₃)₂(i-OC₄H₉)₂), trimethoxy isobutoxy titanium(Ti(OCH₃)₃(i-OC₄H₉)), triisobutoxy ethoxy titanium(Ti(OCH₃CH₂)(i-OC₄H₉)₃), diisobutoxy diethoxy titanium(Ti(OCH₃CH₂)₂(i-OC₄H₉)₂), triethoxy isobutoxy titanium(Ti(OCH₃CH₂)₃(i-OC₄H₉)), tri-n-butoxy methoxy titanium(Ti(OCH₃)(OC₄H₉)₃), din-butoxy dimethoxy titanium (Ti(OCH₃)₂(OC₄H₉)₂),trimethoxy n-butoxy titanium (Ti(OCH₃)₃(OC₄H₉)), tri-n-butoxy methoxytitanium (Ti(OCH₃CH₂)(OC₄H₉)₃), din-butoxy diethoxy titanium(Ti(OCH₃CH₂)₂(OC₄H₉)₂), triethoxy n-butoxy titanium(Ti(OCH₃CH₂)₃(OC₄H₉)), and so on,

tetramethoxy zirconium (Zr(OCH₃)₄), tetraethoxy zirconium(Zr(OCH₃CH₂)₄), tetraisobutoxy zirconium (Zr(i-OC₄H₉)₄), tetran-butoxyzirconium (Zr(OC₄H₉)₄), triethoxy methoxy zirconium(Zr(OCH₃)(OCH₃CH₂)₃), diethoxy dimethoxy zirconium(Zr(OCH₃)₂(OCH₃CH₂)₂), trimethoxy ethoxy zirconium (Zr(OCH₃)₃(OCH₃CH₂)),triisobutoxy methoxy zirconium (Zr(OCH₃)(i-OC₄H₉)₃), diisobutoxydimethoxy zirconium (Zr(OCH₃)₂(i-OC₄H₉)₂), trimethoxy isobutoxyzirconium (Zr(OCH₃)₃(i-C₄H₉)), triisobutoxy ethoxy zirconium(Zr(OCH₃CH₂)(i-OC₄H₉)₃), diisobutoxy diethoxy zirconium(Zr(OCH₃CH₂)₂(i-OC₄H₉)₂), triethoxy isobutoxy zirconium(Zr(OCH₃CH₂)₃(i-OC₄H₉)), tri-n-butoxy methoxy zirconium(Zr(OCH₃)(OC₄H₉)₃), din-butoxy dimethoxy zirconium (Zr(OCH₃)₂(OC₄H₉)₂),trimethoxy n-butoxy zirconium (Zr(OCH₃)₃(OC₄H₉)), tri-n-butoxy methoxyzirconium (Zr(OCH₃CH₂)(OC₄H₉)₃), din-butoxy diethoxy zirconium(Zr(OCH₃CH₂)₂(OC₄H₉)₂), triethoxy n-butoxy zirconium(Zr(OCH₃CH₂)₃(OC₄H₉)), and so on,

tetramethoxy hafnium (Hf(OCH₃)₄), tetraethoxy hafnium (Hf(OCH₃CH₂)₄),tetraisobutoxy hafnium (Hf(i-OC₄H₉)₄), tetran-butoxy hafnium(Hf(OC₄H₉)₄), triethoxy methoxy hafnium (Hf(OCH₃)(OCH₃CH₂)₃), diethoxydimethoxy hafnium (Hf(OCH₃)₂(OCH₃CH₂)₂), trimethoxy ethoxy hafnium(Hf(OCH₃)₃(OCH₃CH₂)), triisobutoxy methoxy hafnium (Hf(OCH₃)(i-OC₄H₉)₃),diisobutoxy dimethoxy hafnium (Hf(OCH₃)₂(i-OC₄H₉)₂), trimethoxyisobutoxy hafnium (Hf(OCH₃)₃(i-OC₄H₉)), triisobutoxy ethoxy hafnium(Hf(OCH₃CH₂)(i-OC₄H₉)₃), diisobutoxy diethoxy hafnium(Hf(OCH₃CH₂)₂(i-OC₄H₉)₂), triethoxy isobutoxy hafnium(Hf(OCH₃CH₂)₃(i-C₄H₉)), tri-n-butoxy methoxy hafnium (Hf(OCH₃)(OC₄H₉)₃),din-butoxy dimethoxy hafnium (Hf(OCH₃)₂(OC₄H₉)₂), trimethoxy n-butoxyhafnium (Hf(OCH₃)₃(OC₄H₉)), tri-n-butoxy methoxy hafnium(Hf(OCH₃CH₂)(OC₄H₉)₃), din-butoxy diethoxy hafnium(Hf(OCH₃CH₂)₂(OC₄H₉)₂), triethoxy n-butoxy hafnium(Hf(OCH₃CH₂)₃(OC₄H₉)), and so on.

As the Group IVB metal alkyl halide, exemplified is trimethyl chlorotitanium (TiCl(CH₃)₃), triethyl chloro titanium (TiCl(CH₃CH₂)₃),triisobutyl chloro titanium (TiCl(i-C₄H₉)₃), trin-butyl chloro titanium(TiCl(C₄H₉)₃), dimethyl dichloro titanium (TiCl₂(CH₃)₂), diethyldichloro titanium (TiCl₂(CH₃CH₂)₂), diisobutyl dichloro titanium(TiCl₂(i-C₄₋₉)₂), trin-butyl chloro titanium (TiCl(C₄H₉)₃), methyltrichloro titanium (Ti(CH₃)Cl₃), ethyl trichloro titanium(Ti(CH₃CH₂)Cl₃), isobutyl trichloro titanium (Ti(i-C₄H₉)Cl₃), n-butyltrichloro titanium (Ti(C₄H₉)Cl₃),

trimethyl bromo titanium (TiBr(CH₃)₃), triethyl bromo titanium(TiBr(CH₃CH₂)₃), triisobutyl bromo titanium (TiBr(i-C₄H₉)₃), trin-butylbromo titanium (TiBr(C₄H₉)₃), dimethyl dibromo titanium (TiBr₂(CH₃)₂),diethyl dibromo titanium (TiBr₂(CH₃CH₂)₂), diisobutyl dibromo titanium(TiBr₂(i-C₄H₉)₂), trin-butyl bromo titanium (TiBr(C₄H₉)₃), methyltribromo titanium (Ti(CH₃)Br₃), ethyl tribromo titanium (Ti(CH₃CH₂)Br₃),isobutyl tribromo titanium (Ti(i-C₄H₉)Br₃), n-butyl tribromo titanium(Ti(C₄H₉)Br₃),

trimethyl chloro zirconium (ZrCl(CH₃)₃), triethyl chloro zirconium(ZrCl(CH₃CH₂)₃), triisobutyl chloro zirconium (ZrCl(i-C₄H₉)₃),trin-butyl chloro zirconium (ZrCl(C₄H₉)₃), dimethyl dichloro zirconium(ZrCl₂(CH₃)₂), diethyl dichloro zirconium (ZrCl₂(CH₃CH₂)₂), diisobutyldichloro zirconium (ZrCl₂(i-C₄H₉)₂), trin-butyl chloro zirconium(ZrCl(C₄H₉)₃), methyl trichloro zirconium (Zr(CH₃)Cl₃), ethyl trichlorozirconium (Zr(CH₃CH₂)Cl₃), isobutyl trichloro zirconium (Zr(i-C₄H₉)Cl₃),n-butyl trichloro zirconium (Zr(C₄H₉)Cl₃),

trimethyl bromo zirconium (ZrBr(CH₃)₃), triethyl bromo zirconium(ZrBr(CH₃CH₂)₃), triisobutyl bromo zirconium (ZrBr(i-C₄H₉)₃), trin-butylbromo zirconium (ZrBr(C₄H₉)₃), dimethyl dibromo zirconium (ZrBr₂(CH₃)₂),diethyl dibromo zirconium (ZrBr₂(CH₃CH₂)₂), diisobutyl dibromo zirconium(ZrBr₂(i-C₄H₉)₂), trin-butyl bromo zirconium (ZrBr(C₄H₉)₃), methyltribromo zirconium (Zr(CH₃)Br₃), ethyl tribromo zirconium(Zr(CH₃CH₂)Br₃), isobutyl tribromo zirconium (Zr(i-C₄H₉)Br₃), n-butyltribromo zirconium (Zr(C₄H₉)Br₃),

trimethyl chloro hafnium (HfCl(CH₃)₃), triethyl chloro hafnium(HfCl(CH₃CH₂)₃), triisobutyl chloro hafnium (HfCl(i-C₄H₉)₃), trin-butylchloro hafnium (HfCl(C₄H₉)₃), dimethyl dichloro hafnium (HfCl₂(CH₃)₂),diethyl dichloro hafnium (HfCl₂(CH₃CH₂)₂), diisobutyl dichloro hafnium(HfCl₂(i-C₄H₉)₂), trin-butyl chloro hafnium (HfCl(C₄H₉)₃), methyltrichloro hafnium (Hf(CH₃)Cl₃), ethyl trichloro hafnium (Hf(CH₃CH₂)Cl₃),isobutyl trichloro hafnium (Hf(i-C₄H₉)Cl₃), n-butyl trichloro hafnium(Hf(C₄H₉)Cl₃),

trimethyl bromo hafnium (HfBr(CH₃)₃), triethyl bromo hafnium(HfBr(CH₃CH₂)₃), triisobutyl bromo hafnium (HfBr(i-C₄H₉)₃), trin-butylbromo hafnium (HfBr(C₄H₉)₃), dimethyl dibromo hafnium (HfBr₂(CH₃)₂),diethyl dibromo hafnium (HfBr₂(CH₃CH₂)₂), diisobutyl dibromo hafnium(HfBr₂(i-C₄H₉)₂), trin-butyl bromo hafnium (HfBr(C₄H₉)₃), methyltribromo hafnium (Hf(CH₃)Br₃), ethyl tribromo hafnium (Hf(CH₃CH₂)Br₃),isobutyl tribromo hafnium (Hf(i-C₄H₉)Br₃), n-butyl tribromo hafnium(Hf(C₄H₉)Br₃).

As the Group IVB metal alkoxy halide, exemplified is trimethoxy chlorotitanium (TiCl(OCH₃)₃), triethoxy chloro titanium (TiCl(OCH₃CH₂)₃),triisobutoxy chloro titanium (TiCl(i-OC₄H₉)₃), tri-n-butoxy chlorotitanium (TiCl(OC₄H₉)₃), dimethoxy dichloro titanium (TiCl₂(OCH₃)₂),diethoxy dichloro titanium (TiCl₂(OCH₃CH₂)₂), diisobutoxy dichlorotitanium (TiCl₂(i-OC₄H₉)₂), tri-n-butoxy chloro titanium (TiCl(OC₄H₉)₃),methoxy trichloro titanium (Ti(OCH₃)Cl₃), ethoxy trichloro titanium(Ti(OCH₃CH₂)Cl₃), isobutoxy trichloro titanium (Ti(i-C₄H₉)Cl₃), n-butoxytrichloro titanium (Ti(OC₄H₉)Cl₃),

trimethoxy bromo titanium (TiBr(OCH₃)₃), triethoxy bromo titanium(TiBr(OCH₃CH₂)₃), triisobutoxy bromo titanium (TiBr(i-OC₄H₉)₃),tri-n-butoxy bromo titanium (TiBr(OC₄H₉)₃), dimethoxy dibromo titanium(TiBr₂(OCH₃)₂), diethoxy dibromo titanium (TiBr₂(OCH₃CH₂)₂), diisobutoxydibromo titanium (TiBr₂(i-OC₄H₉)₂), tri-n-butoxy bromo titanium(TiBr(OC₄H₉)₃), methoxy tribromo titanium (Ti(OCH₃)Br₃), ethoxy tribromotitanium (Ti(OCH₃CH₂)Br₃), isobutoxy tribromo titanium (Ti(i-C₄H₉)Br₃),n-butoxy tribromo titanium (Ti(OC₄H₉)Br₃),

trimethoxy chloro zirconium (ZrCl(OCH₃)₃), triethoxy chloro zirconium(ZrCl(OCH₃CH₂)₃), triisobutoxy chloro zirconium (ZrCl(i-OC₄H₉)₃),tri-n-butoxy chloro zirconium (ZrCl(OC₄H₉)₃), dimethoxy dichlorozirconium (ZrCl₂(OCH₃)₂), diethoxy dichloro zirconium (ZrCl₂(OCH₃CH₂)₂),diisobutoxy dichloro zirconium (ZrCl₂(i-OC₄H₉)₂), tri-n-butoxy chlorozirconium (ZrCl(OC₄H₉)₃), methoxy trichloro zirconium (Zr(OCH₃)Cl₃),ethoxy trichloro zirconium (Zr(OCH₃CH₂)Cl₃), isobutoxy trichlorozirconium (Zr(i-C₄H₉)Cl₃), n-butoxy trichloro zirconium (Zr(OC₄H₉)Cl₃),

trimethoxy bromo zirconium (ZrBr(OCH₃)₃), triethoxy bromo zirconium(ZrBr(OCH₃CH₂)₃), triisobutoxy bromo zirconium (ZrBr(i-OC₄H₉)₃),tri-n-butoxy bromo zirconium (ZrBr(OC₄H₉)₃), dimethoxy dibromo zirconium(ZrBr₂(OCH₃)₂), diethoxy dibromo zirconium (ZrBr₂(OCH₃CH₂)₂),diisobutoxy dibromo zirconium (ZrBr₂(i-OC₄H₉)₂), tri-n-butoxy bromozirconium (ZrBr(OC₄H₉)₃), methoxy tribromo zirconium (Zr(OCH₃)Br₃),ethoxy tribromo zirconium (Zr(OCH₃CH₂)Br₃), isobutoxy tribromo zirconium(Zr(i-C₄H₉)Br₃), n-butoxy tribromo zirconium (Zr(OC₄H₉)Br₃),

trimethoxy chloro hafnium (HfCl(OCH₃)₃), triethoxy chloro hafnium(HfCl(OCH₃CH₂)₃), triisobutoxy chloro hafnium (HfCl(i-OC₄H₉)₃),tri-n-butoxy chloro hafnium (HfCl(OC₄H₉)₃), dimethoxy dichloro hafnium(HfCl₂(OCH₃)₂), diethoxy dichloro hafnium (HfCl₂(OCH₃CH₂)₂), diisobutoxydichloro hafnium (HfCl₂(i-OC₄H₉)₂), tri-n-butoxy chloro hafnium(HfCl(OC₄H₉)₃), methoxy trichloro hafnium (Hf(OCH₃)Cl₃), ethoxytrichloro hafnium (Hf(OCH₃CH₂)Cl₃), isobutoxy trichloro hafnium(Hf(i-C₄H₉)Cl₃), n-butoxy trichloro hafnium (Hf(OC₄H₉)Cl₃),

trimethoxy bromo hafnium (HfBr(OCH₃)₃), triethoxy bromo hafnium(HfBr(OCH₃CH₂)₃), triisobutoxy bromo hafnium (HfBr(i-OC₄H₉)₃),tri-n-butoxy bromo hafnium (HfBr(OC₄H₉)₃), dimethoxy dibromo hafnium(HfBr₂(OCH₃)₂), diethoxy dibromo hafnium (HfBr₂(OCH₃CH₂)₂), diisobutoxydibromo hafnium (HfBr₂(i-OC₄H₉)₂), tri-n-butoxy bromo hafnium(HfBr(OC₄H₉)₃), methoxy tribromo hafnium (Hf(OCH₃)Br₃), ethoxy tribromohafnium (Hf(OCH₃CH₂)Br₃), isobutoxy tribromo hafnium (Hf(i-C₄H₉)Br₃),n-butoxy tribromo hafnium (Hf(OC₄H₉)Br₃).

As the Group IVB metal compound, preference is given to the Group IVBmetal halide, such as TiCl₄, TiBr₄, ZrCl₄, ZrBr₄, HfCl₄ and HfBr₄, suchas TiCl₄ and ZrCl₄.

The Group IVB metal compound could be used with one kind or as a mixtureof two or more kinds at any ratio therebetween.

When the chemical treating agent presents as a liquid at the normaltemperature, the chemical treating agent can be used by directlydropwise adding a predetermined amount of the chemical treating agent toa reaction subject to be treated with said chemical treating agent (i.e.the aforesaid modified carrier).

When the chemical treating agent presents a solid at the normaltemperature, for ease of metering and handling, it is preferably to usesaid chemical treating agent in the form of a solution. Of course, whenthe chemical treating agent presents a liquid at the normal temperature,said chemical treating agent can be also used in the form of a solutionif needed, without any specific limitation.

In preparation of the solution of the chemical treating agent, there isno limitation as to the solvent to be used herein, as long as thesolvent is capable of dissolving the chemical treating agent.

Specifically, as the solvent, exemplified is a C₅₋₁₂ alkane or ahalogenated C₅₋₁₂ alkane, for example pentane, hexane, heptane, octane,nonane, decane, undecane, dodecane, cyclohexane, chloro pentane, chlorohexane, chloro heptane, chloro octane, chloro nonane, chloro decane,chloro undecane, chloro dodecane, chloro cyclohexane and so on,preferably pentane, hexane, decane and cyclohexane, most preferablyhexane.

The solvent could be used with one kind or as a mixture of two or morekinds at any ratio therebetween.

It is obvious that a solvent capable of extracting the magnesiumcompound is not used herein to dissolve the chemical treating agent, forexample an ether based solvent, for example tetrahydrofuran.

Further, there is no limitation as to the concentration of the chemicaltreating agent in the solution, which could be determined as needed, aslong as it is sufficient for the solution to deliver the predeterminedamount of the chemical treating agent for the chemical treatment. Asaforesaid, if the chemical treating agent presents as a liquid, it isconvenient to use said chemical treating agent as such for thetreatment, while it is also acceptable to convert it into a solutionbefore use. Generally, the molar concentration of the chemical treatingagent in its solution is, but not limiting to, 0.01 to 1.0 mol/L.

As a process for conducing the chemical treatment, exemplified is aprocess wherein, when a solid chemical treating agent (for exampleZrCl₄) is used, first of all, a solution of the chemical treating agentis prepared, then the chemical treating agent is added (preferablydropwise) at a predetermined amount to the modified carrier to betreated, or when a liquid chemical treating agent (for example TiCl₄) isused, it is acceptable to add (preferably dropwise) a predeterminedamount of the chemical treating agent as such (or after prepared into asolution) to the modified carrier to be treated. Then, the chemicaltreating reaction continues (facilitated by any stirring means, ifnecessary) at a reaction temperature ranging from −30° C. to 60° C.(preferably −20° C. to 30° C.) for 0.5 to 24 hours, preferably 1 to 8hours, more preferably 2 to 6 hours. Then, the resultant is filtrated,washed and dried.

According to this invention, the filtrating, washing (generally for 1 to8 times, preferably 2 to 6 times, most preferably 2 to 4 times) anddrying can be conducted in a conventional manner, wherein the solventfor washing could be the same as that used for dissolving the chemicaltreating agent.

According to this invention, as the amount of the chemical treatingagent to be used, it is preferably that the ratio by molar of themagnesium compound (based on Mg, solid basis) to the chemical treatingagent (based on the Group IVB metal, for example Ti) is 1:0.01-1,preferably 1:0.01-0.50, more preferably 1:0.10-0.30.

According to a further embodiment of this invention, the present processfor producing a supported nonmetallocene catalyst further comprises astep of pre-treating the modified carrier with an assistant chemicaltreating agent selected from the group consisting of an aluminoxane, analkylaluminum and any combination thereof before treating the modifiedcarrier with the chemical treating agent, referred to as thepre-treating step hereinafter. Then, the chemical treating step isconducted by using the chemical treating agent in the same way asaforesaid, with the only difference of replacing the modified carrierwith the thus pre-treated modified carrier.

The assistant chemical treating agent is further described as follows.

According to this invention, as the assistant chemical treating agent,exemplified is aluminoxane and alkylaluminum.

As the aluminoxane, exemplified is a linear aluminoxane((R)(R)Al—(Al(R)—O)_(n)—O—Al(R)(R)) having the following formula (I),and a cyclic aluminoxane (—(Al(R)—O—)_(n+2)—) having the followingformula (II).

wherein the Rs are identical to or different from one another,preferably identical to one another, and each independently is selectedfrom the group consisting of a C₁-C₈ alkyl, preferably methyl, ethyl,and iso-butyl, most preferably methyl, n is an integer of 1 to 50,preferably of 10 to 30.

Specifically, the aluminoxane could be preferably selected from thegroup consisting of methyl aluminoxane, ethyl aluminoxane, isobutylaluminoxane and n-butyl aluminoxane, preferably methyl aluminoxane (MAO)and isobutyl aluminoxane (IBAO).

The aluminoxane could be used with one kind or as a mixture of two ormore kinds at any ratio therebetween.

As the alkylaluminum, exemplified is a compound having a general formula(III) as follows:

Al(R)₃  (III)

wherein the Rs are identical to or different from one another,preferably identical to one another, and is each independently selectedfrom the group consisting of a C₁-C₈ alkyl, preferably methyl, ethyl andiso-butyl, most preferably methyl.

Specifically, the alkylaluminum could be selected from the groupconsisting of trimethyl aluminum (Al(CH₃)₃), triethyl aluminum(Al(CH₃CH₂)₃), tripropyl aluminum (Al(C₃H₇)₃), triisobutyl aluminum(Al(i-C₄H₉)₃), tri-n-butyl aluminum (Al(C₄H₉)₃), triisoamyl aluminum(Al(i-C₅H₁₁)₃), tri-n-amyl aluminum (Al(C₅H₁₁)₃), trihexyl aluminum(Al(C₆H₁₃)₃), tri-iso-hexyl aluminum (Al(i-C₆H₁₃)₃), diethyl methylaluminum (Al(CH₃)(CH₃CH₂)₂) and ethyl dimethyl aluminum(Al(CH₃CH₂)(CH₃)₂), and the like, wherein preference is given totrimethyl aluminum, triethyl aluminum, triisobutyl aluminum andtripropyl aluminum, most preferably triethyl aluminum and triisobutylaluminum.

The alkylaluminum could be used with one kind or as a mixture of two ormore kinds at any ratio therebetween.

According to this invention, as the assistant chemical treating agent,used could be only the alkylaluminum or only the aluminoxane, or anymixture of the alkylaluminum and the aluminoxane. There is no limitationas to the ratio between any two or more components in the mixture, whichcould be determined as needed.

According to this invention, the assistant chemical treating agent isgenerally used in the form of a solution. In preparation of the solutionof the assistant chemical treating agent, there is no limitation as tothe solvent to be used herein, as long as the solvent can dissolve theassistant chemical treating agent.

Specifically, as the solvent, exemplified is a C₅₋₁₂ alkane or ahalogenated C₅₋₁₂ alkane, for example pentane, hexane, heptane, octane,nonane, decane, undecane, dodecane, cyclohexane, chloro pentane, chlorohexane, chloro heptane, chloro octane, chloro nonane, chloro decane,chloro undecane, chloro dodecane, chloro cyclohexane and so on,preferably pentane, hexane, decane and cyclohexane, most preferablyhexane.

It is obvious that a solvent capable of extracting the magnesiumcompound is not used herein to dissolve the assistant chemical treatingagent, for example an ether based solvent, for example tetrahydrofuran.

The solvent could be used with one kind or as a mixture of two or morekinds at any ratio therebetween.

Further, there is no limitation as to the concentration of the assistantchemical treating agent in the solution, which could be determined asneeded, as long as it is sufficient for the solution to deliver apredetermined amount of the assistant chemical treating agent for thepre-treatment.

As a process for conducing the pre-treatment, exemplified is a processwherein, first of all, a solution of the assistant chemical treatingagent is prepared, then at a temperature ranging from −30° C. to 60° C.(preferably −20° C. to 30° C.), the assistant chemical treating agentsolution (containing a predetermined amount of the assistant chemicaltreating agent) is metering (preferably dropwise) into the modifiedcarrier to be pre-treated with said assistant chemical treating agent,or the modified carrier is metering into the assistant chemical treatingagent solution, so as to form a reaction mixture. Then, the reactioncontinues (facilitated by any stirring means, if necessary) for 1 to 8hours, preferably 2 to 6 hours, more preferably 3 to 4 hours. Then, thethus obtained product is separated from the reaction mixture byfiltrating, washing (for 1 to 6 times, preferably 1 to 3 times) andoptional drying. Or alternatively, the thus obtained product is directlyused in the next step (i.e. the aforesaid chemical treating step) in theform of the reaction mixture without being subject to the separationbeforehand. In this case, the reaction mixture contains a certain amountof solvent, and for this reason, the amount of the solvent involved insaid next step could be reduced accordingly.

According to this invention, as the amount of the assistant chemicaltreating agent to be used, it is preferably that the ratio by molar ofthe magnesium compound (based on Mg, on a solid basis) to the assistantchemical treating agent (based on Al) is 1:0-1.0, preferably 1:0-0.5,more preferably 1:0.1-0.5.

It is known that any of the aforementioned processes and steps ispreferably carried out under a substantial water-free and oxygen-freecondition. By substantial water-free and oxygen-free condition, it meansthat water and oxygen in the system concerned is continuously controlledto be less than 10 ppm. Further, the support nonmetallocene catalystaccording to this invention, after prepared, is usually stored under asealed condition under a slightly positive pressure before use.

According to this invention, as the amount of the nonmetallocene complexto be used, it is preferably that the ratio by molar of the magnesiumcompound (based on Mg, on a solid basis) to the nonmetallocene complexis 1:0.01-1, preferably 1:0.04-0.4, more preferably 1:0.08-0.2.

According to this invention, as the amount of the solvent for dissolvingthe magnesium compound to be used, it is preferably that the ratio ofthe magnesium compound (on a solid basis) to the solvent is 1 mol:75˜400ml, preferably 1 mol:150˜300 ml, more preferably 1 mol:200˜250 ml.

According to this invention, as the amount of the precipitating agent tobe used, it is preferably that the ratio by volume of the precipitatingagent to the solvent for dissolving the magnesium compound is 1:0.2-5,preferably 1:0.5-2, more preferably 1:0.8-1.5.

According to this invention, as the amount of the chemical treatingagent to be used, it is preferably that the ratio by molar of themagnesium compound (based on Mg, on a solid basis) to the chemicaltreating agent (based on the Group IVB metal, for example Ti) is1:0.01-1, preferably 1:0.01-0.50, more preferably 1:0.10-0.30.

According to this invention, as the amount of the assistant chemicaltreating agent to be used, it is preferably that the ratio by molar ofthe magnesium compound (based on Mg, on a solid basis) to the assistantchemical treating agent (based on Al) is 1:0-1.0, preferably 1:0-0.5,more preferably 1:0.1-0.5.

In one embodiment, this invention relates to a supported nonmetallocenecatalyst produced in line with the process according to any of the firstto fourth embodiments of this invention, also referred to as a supportednonmetallocene catalyst for olefin polymerization.

In a further embodiment according to this invention, this inventionrelates to an olefin homopolymerization/copolymerization process,wherein the supported nonmetallocene catalyst of this invention is usedas the catalyst for olefin polymerization, to homopolymerize orcopolymerize olefin(s).

In the context of the olefin homopolymerization/copolymerization processof this invention, one can directly refer to the prior art for anycontent or information that has not been expressively and specificallydescribed hereinafter, for example, the reactor for polymerization, theamount of olefin(s), the way by which the catalyst or olefin isintroduced, unnecessiating the need of detailing same further herein.

According to the present olefin homopolymerization/copolymerizationprocess, the supported nonmetallocene catalyst of this invention is usedas the main catalyst, one or more selected from the group consisting ofan aluminoxane, an alkylaluminum, a halogenated alkyl aluminum, afluoroborane, an alkylboron and an alkylboron ammonium salt is used asthe co-catalyst, to homopolymerize or copolymerize olefin.

As the way of adding the main catalyst and the co-catalyst to thepolymerization system, exemplified is a way wherein the main catalyst isadded prior to the co-catalyst, or vise versa, or the main catalyst andthe co-catalyst contact with each other by mixing and then addedaltogether, or separately but simultaneously added. As the way of addingthe main catalyst and the co-catalyst separately, exemplified is thecase wherein the main catalyst and the co-catalyst are successivelyadded to one feed line or multiple feed lines. When the main catalystand the co-catalyst are to be added separately but simultaneously,multiple feed lines are required. For a continuous polymerization, theway of simultaneously and continuously adding to multiple feed lines ispreferred, while for a batch polymerization, the way of mixing the maincatalyst and the co-catalyst with each other and then adding to one feedline altogether, or adding to a feed line the co-catalyst and thenadding the main catalyst to the same feed line, is preferred.

There is no limitation as to how to conduct the olefinhomopolymerization/copolymerization, any conventional process known to aperson skilled in the art can be used, for example, a slurry process, anemulsion process, a solution process, a bulk process or a gas phaseprocess, preferably the slurry process or the gas phase process.

According to this invention, as the olefin to be used, exemplified is aC₂ to C₁₀ mono-olefin, a diolefin, a cyclic olefin and other ethylenicunsaturated compounds.

Specifically, as the C₂ to C₁₀ mono-olefin, exemplified is ethylene,propylene, 1-butene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene,1-decene, 1-undecene, 1-dodecene and styrene. As the cyclic olefin,exemplified is 1-cyclopentene and norbornene. As the diolefin,exemplified is 1,4-butadiene, 2,5-pentadiene, 1,6-hexadiene,norbornadiene and 1,7-octadiene. As the other ethylenic unsaturatedcompound, exemplified is vinyl acetate, and (meth)acrylate. Thisinvention prefers the homopolymerization of ethylene, or thecopolymerization of ethylene with propylene, 1-butene or 1-hexene.

According to this invention, by homopolymerization, it refers to thepolymerization of a single kind of olefin, by copolymerization, itrefers to the polymerization between two or more of the aforesaidolefins.

According to this invention, the co-catalyst is selected from the groupconsisting of an aluminoxane, an alkylaluminum, a halogenated alkylaluminum, a fluoroborane, an alkylboron and an alkylboron ammonium salt,such as the aluminoxane and the alkylaluminum.

As the aluminoxane, exemplified is a linear aluminoxane((R)(R)Al—(Al(R)—O)_(n)—O—Al(R)(R)) having the following formula (I-1),and a cyclic aluminoxane (—(Al(R)—O—)_(n+2)—) having the followingformula (II-1).

wherein the Rs are identical to or different from one another,preferably identical to one another, and each independently is selectedfrom the group consisting of a C₁-C₈ alkyl, preferably methyl, ethyl,and iso-butyl, most preferably methyl, n is an integer of 1 to 50,preferably of 10 to 30.

Specifically, the aluminoxane could be preferably selected from thegroup consisting of methyl aluminoxane, ethyl aluminoxane, isobutylaluminoxane and n-butyl aluminoxane, preferably methyl aluminoxane (MAO)and isobutyl aluminoxane (IBAO), most preferably methyl aluminoxane(MAO).

The aluminoxane could be used with one kind or as a mixture of two ormore kinds at any ratio therebetween.

As the alkylaluminum, exemplified is a compound having a general formula(III-1) as follows:

Al(R)₃  (III-1)

wherein the Rs are identical to or different from one another,preferably identical to one another, and is each independently selectedfrom the group consisting of a C₁-C₈ alkyl, preferably methyl, ethyl andiso-butyl, most preferably methyl.

Specifically, the alkylaluminum could be selected from the groupconsisting of trimethyl aluminum (Al(CH₃)₃), triethyl aluminum(Al(CH₃CH₂)₃), tripropyl aluminum (Al(C₃H₇)₃), triisobutyl aluminum(Al(i-C₄H₉)₃), tri-n-butyl aluminum (Al(C₄H₉)₃), triisoamyl aluminum(Al(i-C₅H₁₁)₃), tri-n-amyl aluminum (Al(C₅H₁₁)₃), tri-hexyl aluminum(Al(C₆H₁₃)₃), tri-iso-hexyl aluminum (Al(i-C₆H₁₃)₃), diethyl methylaluminum (Al(CH₃)(CH₃CH₂)₂) and ethyl dimethyl aluminum(Al(CH₃CH₂)(CH₃)₂), and the like, wherein preference is given totrimethyl aluminum, triethyl aluminum, triisobutyl aluminum andtripropyl aluminum, more preferably triethyl aluminum and triisobutylaluminum, most preferably triethyl aluminum.

The alkylaluminum could be used with one kind or as a mixture of two ormore kinds at any ratio therebetween.

As the halogenated alkyl aluminum, the fluoroborane, the alkylboron andthe alkylboron ammonium salt, exemplified is one conventionally used inthis field, but without any limitation thereto.

Further, according to this invention, the co-catalyst could be used withone kind or as a mixture of two or more kinds of the aforesaidco-catalysts at any ratio therebetween as needed, but without anylimitation thereto.

According to this invention, depending on how the olefinhomopolymerization/copolymerization is conducted, a solvent forpolymerization may be involved.

As the solvent for polymerization, one conventionally used in this fieldfor olefin homopolymerization/copolymerization can be used, but withoutany limitation thereto.

As the solvent for polymerization, exemplified is a C₄₋₁₀ alkane (forexample, butane, pentane, hexane, heptane, octane, nonane, or decane), ahalogenated C₁₋₁₀ alkane (for example, dichloro methane), an aromatichydrocarbon based solvent (for example toluene or xylene), and so on.Hexane is preferred for this purpose.

The solvent for polymerization could be used with one kind or as amixture of two or more kinds at any ratio therebetween.

According to this invention, the polymerization pressure under which theolefin homopolymerization/copolymerization is conducted is generallybetween 0.1 to 10 MPa, preferably 0.1 to 4 MPa, most preferably 1 to 3MPa, but without any limitation thereto. According to this invention,the polymerization temperature at which the olefinhomopolymerization/copolymerization is conducted is generally from −40°C. to 200° C., preferably 10° C. to 100° C., more preferably 40° C. to90° C., but without any limitation thereto.

Further, according to this invention, the olefinhomopolymerization/copolymerization can be conduct in the presence of orin the absence of hydrogen gas. If presents, the partial pressure ofhydrogen gas may generally account for 0.01 to 99% (preferably 0.01 to50%) of the polymerization pressure, but without any limitation thereto.

According to the olefin homopolymerization/copolymerization process ofthis invention, the ratio by molar of the co-catalyst (based on Al or B)to the supported nonmetallocene catalyst (based on the central metalatom M) is generally 1 to 1000:1, preferably 10 to 500:1, morepreferably 15 to 300:1, but without any limitation thereto.

Example

The present invention is further illustrated by using the followingexamples, not limiting to same.

The bulk density of the polymer was measured according to the ChineseStandard GB 1636-79 (unit: g/cm³).

The content of the Group IVB metal (for example Ti) and the content ofthe Mg element in the supported nonmetallocene catalyst were determinedby the ICP-AES method, while the content of the nonmetallocene ligandwas determined by the element analysis method.

The polymerization activity of the catalyst was calculated as follows.

Upon completion of the polymerization, the polymer product in thereactor was filtered and dried, and then weighed for its weight (bymass). Then, the polymerization activity of the catalyst was expressedby a value obtained by dividing the weight of the polymer product by theweight (by mass) of the supported nonmetallocene catalyst used (unit: kgpolymer per 1 g Cat).

The molecular weights Mw, Mn and the molecular weight distribution(Mw/Mn) of the polymer were determined at a temperature of 150° C. byusing the GPC V2000 type gel permeation chromatographer (from WATERSCo., USA), with o-trichlorobenzene as the solvent.

The viscosity averaged molecular weight of the polymer was calculated asfollows.

The intrinsic viscosity of the polymer was determined according to thestandard ASTM D4020-00 by using a high temperature dilution typeUbbelohde viscometer (with a capillary inner diameter of 0.44 mm, athermostatic bath media of 300# silicon oil, the solvent for dilution ofdecalin and a temperature of 135° C.), and then the viscosity averagedmolecular weight Mv of the polymer was calculated in line with thefollowing formula.

Mv=5.37×10⁴×[η]^(1.37)

wherein, η is the intrinsic viscosity.

Example I Corresponding to the First Embodiment Example I-1

Anhydrous magnesium chloride was used as the magnesium compound,tetrahydrofuran was used as the solvent for dissolving the magnesiumcompound and the nonmetallocene complex, the compound represented by

was used as the nonmetallocene complex.

5 g of the anhydrous magnesium chloride and the nonmetallocene complexwere weighted, tetrahydrofuran was added thereto to completely dissolvesame at the normal temperature. After stirring for 2 hours, theresultant was uniformly heated to 90° C. and directly vacuum dried, toobtain the supported nonmetallocene catalyst.

In this example, the ratio of magnesium chloride to tetrahydrofuran was1 mol:210 ml, the ratio by molar of magnesium chloride to thenonmetallocene complex was 1:0.08.

The thus obtained supported nonmetallocene catalyst was named asCAT-I-1.

Example I-2

Substantially the same as the Example I-1, except for the followingchanges:

The nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to toluene, and the magnesium compound solution wasvacuum dried at 100° C.

In this example, the ratio of the magnesium compound to toluene was 1mol:150 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.15.

The thus obtained supported nonmetallocene catalyst was named asCAT-I-2.

Example I-3

Substantially the same as the Example I-1, except for the followingchanges:

The magnesium compound was changed to anhydrous magnesium bromide(MgBr₂), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to ethyl benzene, and the magnesium compoundsolution was vacuum dried at 110° C.

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:250 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.20.

The thus obtained supported nonmetallocene catalyst was named asCAT-I-3.

Example I-4

Substantially the same as the Example I-1, except for the followingchanges:

The magnesium compound was changed to ethoxy magnesium chloride(MgCl(OC₂H₅)), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to xylene, and the magnesium compound solution wasvacuum dried at 150° C.

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:300 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.04.

The thus obtained supported nonmetallocene catalyst was named asCAT-I-4.

Example I-5

Substantially the same as the Example I-1, except for the followingchanges:

The magnesium compound was changed to butoxy magnesium bromide(MgBr(OC₄H₉)), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to diethyl benzene, and the magnesium compoundsolution was vacuum dried at 110° C.

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:400 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.30.

The thus obtained supported nonmetallocene catalyst was named asCAT-I-5.

Example I-6

Substantially the same as the Example I-1, except for the followingchanges:

The magnesium compound was changed to methyl magnesium chloride(Mg(CH₃)Cl), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to chloro toluene, and the magnesium compoundsolution was vacuum dried at 120° C.

In this example, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.10.

The thus obtained supported nonmetallocene catalyst was named asCAT-I-6.

Example I-7

Substantially the same as the Example I-1, except for the followingchanges:

The magnesium compound was changed to ethyl magnesium chloride(Mg(C₂H₅)Cl), the nonmetallocene complex was changed to

and the magnesium compound solution was vacuum dried at 60° C.

The thus obtained supported nonmetallocene catalyst was named asCAT-I-7.

Example I-8

Substantially the same as the Example I-1, except for the followingchanges:

The magnesium compound was changed to ethyl magnesium (Mg(C₂H₅)₂), thenonmetallocene complex was changed to

The thus obtained supported nonmetallocene catalyst was named asCAT-I-8.

Example I-9

Substantially the same as the Example I-1, except for the followingchanges:

The magnesium compound was changed to methyl ethoxy magnesium(Mg(OC₂H₅)(CH₃)).

The thus obtained supported nonmetallocene catalyst was named asCAT-I-9.

Example I-10

Substantially the same as the Example I-1, except for the followingchanges:

The magnesium compound was changed to ethyl n-butoxy magnesium(Mg(OC₄H₉)(C₂H₅)).

The thus obtained supported nonmetallocene catalyst was named asCAT-I-10.

Reference Example I-1-A

Substantially the same as the Example I-1, except for the followingchanges:

The ratio by molar of magnesium chloride to the nonmetallocene complexwas changed to 1:0.16.

The thus obtained catalyst was named as CAT-I-1-A.

Reference Example I-1-B

Substantially the same as the Example I-1, except for the followingchanges:

The ratio by molar of magnesium chloride to the nonmetallocene complexwas changed to 1:0.04.

The thus obtained catalyst was named as CAT-I-1-B.

Reference Example I-1-C

Substantially the same as the Example I-1, except for the followingchanges:

In preparation of the catalyst, 60 ml hexane was added to the magnesiumcompound solution to precipitate same, which was then filtered, washedwith hexane for 3 times (60 ml per time), and finally vacuum dried at60° C.

The thus obtained catalyst was named as CAT-I-1-C.

Reference Example I-1-D

Substantially the same as the Example I-1, except for the followingchanges:

The nonmetallocene complex was changed to the following nonmetalloceneligand.

The thus obtained catalyst was named as CAT-I-1-D.

Application Example I

The catalysts CAT-I-1 to CAT-I-9, CAT-I-1-A to CAT-I-1-D obtained fromthe aforesaid Example I series were used for ethylene homopolymerizationor copolymerization under the following conditions according to thefollowing processes respectively.

Homopolymerization: an autoclave for polymerization (5 L), a slurrypolymerization process, hexane (2.5 L) as the solvent, a totalpolymerization pressure of 1.5 MPa, a polymerization temperature of 85°C., a ratio by molar of the co-catalyst to the active metal in thecatalyst of 200, a polymerization time of 2 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 50 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto, and ethylene was continuously supplied thereto to keepthe total polymerization pressure constant at 1.5 MPa. Upon completionof the polymerization, the inside of the autoclave was vented to theatmosphere, and the resultant polymer product was discharged from theautoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table I-1.

Copolymerization: an autoclave for polymerization (5 L), a slurrypolymerization process, hexane (2.5 L) as the solvent, a totalpolymerization pressure of 1.5 MPa, a polymerization temperature of 85°C., a ratio by molar of the co-catalyst to the active metal in thecatalyst of 200, a polymerization time of 2 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 50 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto. Hexene-1 (50 g) was added thereto all at once as thecomonomer. Ethylene was continuously supplied thereto to keep the totalpolymerization pressure constant at 1.5 MPa. Upon completion of thepolymerization, the inside of the autoclave was vented to theatmosphere, and the resultant polymer product was discharged from theautoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table I-1.

TABLE I-1 The results of the olefin polymerization obtained with thesupported nonmetallocene catalysts Poly Molecular Exper- activity weightiment (kgPE/ distri- No. Catalyst No. Co-catalyst type gCat) bution 1CAT-I-1 methyl homopoly- 4.29 2.32 aluminoxane merization 2 CAT-I-1methyl copolymeri- 6.44 2.45 aluminoxane zation 3 CAT-I-1 triethylhomopoly- 2.16 2.70 aluminum merization 4 CAT-I-2 methyl homopoly- 5.452.37 aluminoxane merization 5 CAT-I-3 methyl homopoly- 8.51 2.52aluminoxane merization 6 CAT-I-4 methyl homopoly- 3.38 2.38 aluminoxanemerization 7 CAT-I-5 methyl homopoly- 3.53 2.45 aluminoxane merization 8CAT-I-6 methyl homopoly- 5.01 2.33 aluminoxane merization 9 CAT-I-7methyl homopoly- 3.79 2.42 aluminoxane merization 10 CAT-I-8 methylhomopoly- 3.30 2.36 aluminoxane merization 11 CAT-I-9 methyl homopoly-3.59 2.45 aluminoxane merization 12 CAT-I-1-A methyl homopoly- 7.60 2.26aluminoxane merization 13 CAT-I-1-B methyl homopoly- 2.10 2.32aluminoxane merization 14 CAT-I-1-C methyl homopoly- 3.98 2.31aluminoxane merization 15 CAT-I-1-D methyl homopoly- No — aluminoxanemerization activity

As can be seen from the Table I-1, the polymer obtained from thepolymerization by using the supported nonmetallocene catalyst producedin line with the present process exhibits a narrow molecular weightdistribution. It is well known in this field that polyethylene producedfrom the polymerization by using a Ziegler-Natta catalyst usuallyexhibits a molecular weight distribution of about from 3 to 8.

Upon comparison of the results from the experiment No. 1 and those fromthe experiment Nos. 12 and 13 in the Table I-1, it is clear that theactivity of the catalyst increases or decreases as the amount of thenonmetallocene complex to be introduced into the catalyst increases ordecreases, while the molecular weight distribution of the polymerremains substantially unchanged. This fact indicates that the activityof the supported nonmetallocene catalyst of this invention originatesfrom the nonmetallocene complex, and the performances of the polymerobtained from the polymerization depend on it as well.

Upon comparison of the results from the experiment No. 1 and those fromthe experiment No. 14 in the Table I-1, it is clear that the catalystobtained by directly drying the magnesium compound solution according tothis invention exhibits a significantly higher activity than thatobtained by filtering, washing and drying the magnesium compoundsolution.

As can be seen from the results of the experiment No. 15, the catalystobtained with the case wherein the nonmetallocene ligand was used inpreparation of the supported nonmetallocene catalyst shows no activityfor olefin polymerization. It is know that only a catalyst wherein anonmetallocene ligand and an active metal compound react with each otherto in-situ form a nonmetallocene complex, or a catalyst produced bydirectly supporting a nonmetallocene complex, shows an activity forolefin polymerization, while that containing only a nonmetalloceneligand without an active metal element does not.

Example II Corresponding to the Second Embodiment Example II-1

Anhydrous magnesium chloride was used as the magnesium compound,tetrahydrofuran was used as the solvent for dissolving the magnesiumcompound and the nonmetallocene complex, the compound represented by

was used as the nonmetallocene complex.

5 g of the anhydrous magnesium chloride and the nonmetallocene complexwere weighted, tetrahydrofuran was added thereto to completely dissolvesame at the normal temperature. After stirring for 2 hours, hexane (asthe precipitating agent) was added thereto to precipitate same. Theresultant solid was then filtered, washed by a solvent for washing(which is the same as the precipitating agent) for 2 times (by using thesame amount as that of the precipitating agent each time) and thenuniformly heated to 90° C. and vacuum dried, to obtain the supportednonmetallocene catalyst.

In this example, the ratio of magnesium chloride to tetrahydrofuran was1 mol:210 ml, the ratio by molar of magnesium chloride to thenonmetallocene complex was 1:0.08, and the ratio by volume of theprecipitating agent to tetrahydrofuran was 1:1.

The thus obtained supported nonmetallocene catalyst was named asCAT-II-1.

Example II-2

Substantially the same as the Example II-1, except for the followingchanges:

The nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to toluene, and the precipitating agent was changedto cyclohexane.

In this example, the ratio of the magnesium compound to toluene was 1mol:150 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.15, and the ratio by volume of theprecipitating agent to the solvent for dissolving the magnesium compoundand the nonmetallocene complex was 1:2.

The thus obtained supported nonmetallocene catalyst was named asCAT-II-2.

Example II-3

Substantially the same as the Example II-1, except for the followingchanges:

The magnesium compound was changed to anhydrous magnesium bromide(MgBr₂), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to ethyl benzene, and the precipitating agent waschanged to cycloheptane.

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:250 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.20, and the ratio by volume of theprecipitating agent to the solvent for dissolving the magnesium compoundand the nonmetallocene complex was 1:0.70.

The thus obtained supported nonmetallocene catalyst was named asCAT-II-3.

Example II-4

Substantially the same as the Example II-1, except for the followingchanges:

The magnesium compound was changed to ethoxy magnesium chloride(MgCl(OC₂H₅)), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to xylene, and the precipitating agent was changedto decane.

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:300 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.04, and the ratio by volume of theprecipitating agent to the solvent for dissolving the magnesium compoundand the nonmetallocene complex was 1:1.5.

The thus obtained supported nonmetallocene catalyst was named asCAT-II-4.

Example II-5

Substantially the same as the Example II-1, except for the followingchanges:

The magnesium compound was changed to butoxy magnesium bromide(MgBr(OC₄H₉)), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to diethyl benzene.

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:400 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.30.

The thus obtained supported nonmetallocene catalyst was named asCAT-II-5.

Example II-6

Substantially the same as the Example II-1, except for the followingchanges:

The magnesium compound was changed to methyl magnesium chloride(Mg(CH₃)Cl), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to chloro toluene.

In this example, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.10.

The thus obtained supported nonmetallocene catalyst was named asCAT-II-6.

Example II-7

Substantially the same as the Example II-1, except for the followingchanges:

The magnesium compound was changed to ethyl magnesium chloride(Mg(C₂H₅)Cl), the nonmetallocene complex was changed to

The thus obtained supported nonmetallocene catalyst was named asCAT-II-7.

Example II-8

Substantially the same as the Example II-1, except for the followingchanges:

The magnesium compound was changed to ethyl magnesium (Mg(C₂H₅)₂), thenonmetallocene complex was changed to

The thus obtained supported nonmetallocene catalyst was named asCAT-II-8.

Example II-9

Substantially the same as the Example II-1, except for the followingchanges:

The magnesium compound was changed to methyl ethoxy magnesium(Mg(OC₂H₅)(CH₃)).

The thus obtained supported nonmetallocene catalyst was named asCAT-II-9.

Example II-10

Substantially the same as the Example II-1, except for the followingchanges:

The magnesium compound was changed to ethyl n-butoxy magnesium(Mg(OC₄H₉)(C₂H₅)).

The thus obtained supported nonmetallocene catalyst was named asCAT-II-10.

Reference Example II-1-A

Substantially the same as the Example II-1, except for the followingchanges:

The ratio by molar of magnesium chloride to the nonmetallocene complexwas changed to 1:0.16.

The thus obtained catalyst was named as CAT-II-1-A.

Reference Example II-1-B

Substantially the same as the Example II-1, except for the followingchanges:

The ratio by molar of magnesium chloride to the nonmetallocene complexwas changed to 1:0.04.

The thus obtained catalyst was named as CAT-II-1-B.

Reference Example II-1-C

Substantially the same as the Example II-1, except for the followingchanges:

The nonmetallocene complex was changed to the following nonmetalloceneligand.

The thus obtained catalyst was named as CAT-II-1-C.

Application Example II

The catalysts CAT-II-1 to CAT-II-9, CAT-II-1-A to CAT-II-1-C obtainedfrom the aforesaid Example II series were used for ethylenehomopolymerization or copolymerization under the following conditionsaccording to the following processes respectively.

Homopolymerization: an autoclave for polymerization (5 L), a slurrypolymerization process, hexane (2.5 L) as the solvent, a totalpolymerization pressure of 1.5 MPa, a polymerization temperature of 85°C., a ratio by molar of the co-catalyst to the active metal in thecatalyst of 200, a polymerization time of 2 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 50 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto, and ethylene was continuously supplied thereto to keepthe total polymerization pressure constant at 1.5 MPa. Upon completionof the polymerization, the inside of the autoclave was vented to theatmosphere, and the resultant polymer product was discharged from theautoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table II-1.

Copolymerization: an autoclave for polymerization (5 L), a slurrypolymerization process, hexane (2.5 L) as the solvent, a totalpolymerization pressure of 1.5 MPa, a polymerization temperature of 85°C., a ratio by molar of the co-catalyst to the active metal in thecatalyst of 200, a polymerization time of 2 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 50 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto. Hexene-1 (50 g) was added thereto all at once as thecomonomer. Ethylene was continuously supplied thereto to keep the totalpolymerization pressure constant at 1.5 MPa. Upon completion of thepolymerization, the inside of the autoclave was vented to theatmosphere, and the resultant polymer product was discharged from theautoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table II-1.

TABLE II-1 The results of the olefin polymerization obtained with thesupported nonmetallocene catalysts Poly Molecular Exper- activity weightiment (kgPE/ distri- No. Catalyst No. Co-catalyst type gCat) bution 1CAT-II-1 methyl homopoly- 3.98 2.31 aluminoxane merization 2 CAT-II-1methyl copolymeri- 5.93 2.45 aluminoxane zation 3 CAT-II-1 triethylhomopoly- 2.00 2.70 aluminum merization 4 CAT-II-2 methyl homopoly- 5.012.37 aluminoxane merization 5 CAT-II-3 methyl homopoly- 7.90 2.52aluminoxane merization 6 CAT-II-4 methyl homopoly- 3.13 2.38 aluminoxanemerization 7 CAT-II-5 methyl homopoly- 3.27 2.45 aluminoxane merization8 CAT-II-6 methyl homopoly- 4.62 2.33 aluminoxane merization 9 CAT-II-7methyl homopoly- 3.51 2.42 aluminoxane merization 10 CAT-II-8 methylhomopoly- 3.06 2.36 aluminoxane merization 11 CAT-II-9 methyl homopoly-3.33 2.45 aluminoxane merization 12 CAT-II-1-A methyl homopoly- 6.852.26 aluminoxane merization 13 CAT-II-1-B methyl homopoly- 1.95 2.32aluminoxane merization 14 CAT-II-1-C methyl homopoly- No — aluminoxanemerization activity

As can be seen from the Table II-1, the polymer obtained from thepolymerization by using the supported nonmetallocene catalyst producedin line with the present process exhibits a narrow molecular weightdistribution. It is well known in this field that polyethylene producedfrom the polymerization by using a Ziegler-Natta catalyst usuallyexhibits a molecular weight distribution of about from 3 to 8.

Upon comparison of the results from the experiment No. 1 and those fromthe experiment Nos. 12 and 13 in the Table II-1, it is clear that theactivity of the catalyst increases or decreases as the amount of thenonmetallocene complex to be introduced into the catalyst increases ordecreases, while the molecular weight distribution of the polymerremains substantially unchanged. This fact indicates that the activityof the supported nonmetallocene catalyst of this invention originatesfrom the nonmetallocene complex, and the performances of the polymerobtained from the polymerization depend on it as well.

As can be seen from the results of the experiment No. 14, just like theexperiment No. 15 in the Table I-1, the catalyst obtained with the casewherein a nonmetallocene ligand was used in preparation of the supportednonmetallocene catalyst shows no activity for olefin polymerization.

Example III Corresponding to the Third Embodiment Example II-1

Anhydrous magnesium chloride was used as the magnesium compound,tetrahydrofuran was used as the solvent for dissolving the magnesiumcompound and the nonmetallocene complex, titanium tetrachloride was usedas the chemical treating agent, the compound represented by

was used as the nonmetallocene complex.

5 g of the anhydrous magnesium chloride and the nonmetallocene complexwere weighted, tetrahydrofuran was added thereto to completely dissolvesame at the normal temperature. After stirring for 2 hours, theresultant was uniformly heated to 60° C. and directly vacuum dried, toobtain the modified carrier.

Then, to the modified carrier, 60 ml hexane was added, and then titaniumtetrachloride was dropwise added thereto under stirring over a period of30 minutes. The reaction continued at 60° C. under stirring for 4 hours,then filtered, washed with hexane for 2 times (60 ml each time), andvacuum dried at the normal temperature to obtain the supportednonmetallocene catalyst.

In this example, the ratio of magnesium chloride to tetrahydrofuran was1 mol:210 ml, the ratio by molar of magnesium chloride to thenonmetallocene complex was 1:0.08, and the ratio by molar of magnesiumchloride to titanium tetrachloride was 1:0.15.

The thus obtained supported nonmetallocene catalyst was named asCAT-II-1.

Example III-1-1

Substantially the same as the Example III-1, except for the followingchanges:

The nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to toluene, and the chemical treating agent waschanged to zirconium tetrachloride (ZrCl₄).

The magnesium compound solution was vacuum dried at 90° C.

In this example, the ratio of the magnesium compound to toluene was 1mol:150 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.15, and the ratio by molar of themagnesium compound to the chemical treating agent was 1:0.20.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-1-1.

Example III-1-2

Substantially the same as the Example III-1, except for the followingchanges:

The magnesium compound was changed to anhydrous magnesium bromide(MgBr₂), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to ethyl benzene, and the chemical treating agentwas changed to titanium tetrabromide (TiBr₄).

The magnesium compound solution was vacuum dried at 130° C.

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:250 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.20, and the ratio by molar of themagnesium compound to the chemical treating agent was 1:0.30.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-1-2.

Example III-1-3

Substantially the same as the Example III-1, except for the followingchanges:

The magnesium compound was changed to ethoxy magnesium chloride(MgCl(OC₂H₅)), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to xylene, and the chemical treating agent waschanged to tetraethyl titanium (Ti(CH₃CH₂)₄).

The magnesium compound solution was vacuum dried at 110° C.

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:300 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.04, and the ratio by molar of themagnesium compound to the chemical treating agent was 1:0.05.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-1-3.

Example III-1-4

Substantially the same as the Example III-1, except for the followingchanges:

The magnesium compound was changed to butoxy magnesium bromide(MgBr(OC₄H₉)), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to diethyl benzene, and the chemical treating agentwas changed to tetran-butyl titanium (Ti(C₄H₉)₄).

The magnesium compound solution was vacuum dried at 100° C.

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:400 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.30, and the ratio by molar of themagnesium compound to the chemical treating agent was 1:0.50.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-1-4.

Example III-1-5

Substantially the same as the Example III-1, except for the followingchanges:

The magnesium compound was changed to methyl magnesium chloride(Mg(CH₃)Cl), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to chloro toluene, and the chemical treating agentwas changed to tetraethyl zirconium (Zr(CH₃CH₂)₄).

The magnesium compound solution was vacuum dried at 130° C.

In this example, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.10, and the ratio by molar of themagnesium compound to the chemical treating agent was 1:0.10.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-1-5.

Example III-1-6

Substantially the same as the Example III-1, except for the followingchanges:

The magnesium compound was changed to ethyl magnesium chloride(Mg(C₂H₅)Cl), the nonmetallocene complex was changed to

and the chemical treating agent was changed to tetraethoxy titanium(Ti(OCH₃CH₂)₄).

The thus obtained supported nonmetallocene catalyst was named asCAT-III-1-6.

Example III-1-7

Substantially the same as the Example III-1, except for the followingchanges:

The magnesium compound was changed to ethyl magnesium (Mg(C₂H₅)₂), thenonmetallocene complex was changed to

and the chemical treating agent was changed to isobutyl trichlorotitanium (Ti(i-C₄H₉)Cl₃).

The thus obtained supported nonmetallocene catalyst was named asCAT-III-1-7.

Example III-1-8

Substantially the same as the Example III-1, except for the followingchanges:

The magnesium compound was changed to methyl ethoxy magnesium(Mg(OC₂H₅)(CH₃)), and the chemical treating agent was changed totriisobutoxy chloro titanium (TiCl(i-OC₄H₉)₃).

The thus obtained supported nonmetallocene catalyst was named asCAT-III-1-8.

Example III-1-9

Substantially the same as the Example III-1, except for the followingchanges:

The magnesium compound was changed to ethyl n-butoxy magnesium(Mg(OC₄H₉)(C₂H₅)), and the chemical treating agent was changed todimethoxy dichloro zirconium (ZrCl₂(OCH₃)₂).

The thus obtained supported nonmetallocene catalyst was named asCAT-III-1-9.

Example III-2

Anhydrous magnesium chloride was used as the magnesium compound,tetrahydrofuran was used as the solvent for dissolving the magnesiumcompound and the nonmetallocene complex, titanium tetrachloride was usedas the chemical treating agent, the compound represented by

was used as the nonmetallocene complex.

5 g of the anhydrous magnesium chloride and the nonmetallocene complexwere weighted, tetrahydrofuran was added thereto to completely dissolvesame at the normal temperature. After stirring for 2 hours, theresultant was uniformly heated to 60° C. and directly vacuum dried, toobtain the modified carrier.

Then, to the modified carrier, 60 ml hexane was added, and then triethylaluminum (as the assistant chemical treating agent, at a concentrationof 15 wt % in hexane) was dropwise added thereto under stirring over aperiod of 30 minutes. The reaction continued at 60° C. under stirringfor 4 hours, then filtered, washed with hexane for 2 times (60 ml eachtime), and vacuum dried at the normal temperature.

Then, to the thus pre-treated modified carrier, 60 ml hexane was added,and then titanium tetrachloride was dropwise added thereto understirring over a period of 30 minutes. The reaction continued at 60° C.under stirring for 4 hours, then filtered, washed with hexane for 2times (60 ml each time), and vacuum dried at the normal temperature toobtain the supported nonmetallocene catalyst.

In this example, the ratio of magnesium chloride to tetrahydrofuran was1 mol:210 ml, the ratio by molar of magnesium chloride to thenonmetallocene complex was 1:0.08, the ratio by molar of magnesiumchloride to triethyl aluminum was 1:0.15, and the ratio by molar ofmagnesium chloride to titanium tetrachloride was 1:0.15.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-2.

Example III-2-1

Substantially the same as the Example III-2, except for the followingchanges:

The nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to toluene, the assistant chemical treating agentwas changed to methyl aluminoxane (MAO, a 10 wt % solution in toluene),and the chemical treating agent was changed to zirconium tetrachloride(ZrCl₄).

The magnesium compound solution was vacuum dried at 90° C.

After pre-treated with the assistant chemical treating agent, theresultant was washed with toluene for 3 times.

In this example, the ratio of the magnesium compound to toluene was 1mol:150 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.15, the ratio by molar of the magnesiumcompound to the assistant chemical treating agent was 1:0.15, and theratio by molar of the magnesium compound to the chemical treating agentwas 1:0.20.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-2-1.

Example III-2-2

Substantially the same as the Example III-2, except for the followingchanges:

The magnesium compound was changed to anhydrous magnesium bromide(MgBr₂), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to ethyl benzene, the assistant chemical treatingagent was changed to trimethyl aluminum (Al(CH₃)₃), and the chemicaltreating agent was changed to titanium tetrabromide (TiBr₄).

The magnesium compound solution was vacuum dried at 130° C.

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:250 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.2, the ratio by molar of the magnesiumcompound to the assistant chemical treating agent was 1:0.30, and theratio by molar of the magnesium compound to the chemical treating agentwas 1:0.30.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-2-2.

Example III-2-3

Substantially the same as the Example III-2, except for the followingchanges:

The magnesium compound was changed to ethoxy magnesium chloride(MgCl(OC₂H₅)), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to xylene, the assistant chemical treating agent waschanged to triisobutyl aluminum (Al(i-C₄H₉)₃), and the chemical treatingagent was changed to tetraethyl titanium (Ti(CH₃CH₂)₄).

The magnesium compound solution was vacuum dried at 110° C.

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:300 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.04, the ratio by molar of the magnesiumcompound to the assistant chemical treating agent was 1:0.05, and theratio by molar of the magnesium compound to the chemical treating agentwas 1:0.05.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-2-3.

Example III-2-4

Substantially the same as the Example III-2, except for the followingchanges:

The magnesium compound was changed to butoxy magnesium bromide(MgBr(OC₄H₉)), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to diethyl benzene, the assistant chemical treatingagent was changed to isobutyl aluminoxane, and the chemical treatingagent was changed to tetran-butyl titanium (Ti(C₄H₉)₄).

The magnesium compound solution was vacuum dried at 100° C.

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:400 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.30, the ratio by molar of the magnesiumcompound to the assistant chemical treating agent was 1:0.50, and theratio by molar of the magnesium compound to the chemical treating agentwas 1:0.50.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-2-4.

Example III-2-5

Substantially the same as the Example III-2, except for the followingchanges:

The magnesium compound was changed to methyl magnesium chloride(Mg(CH₃)Cl), the solvent for dissolving the magnesium compound and thenonmetallocene complex was changed to chloro toluene, the assistantchemical treating agent was changed to diethyl methyl aluminum(Al(CH₃)(CH₃CH₂)₂), and the chemical treating agent was changed totetraethyl zirconium (Zr(CH₃CH₂)₄).

The magnesium compound solution was vacuum dried at 130° C.

In this example, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.10, the ratio by molar of the magnesiumcompound to the assistant chemical treating agent was 1:0.10, and theratio by molar of the magnesium compound to the chemical treating agentwas 1:0.10.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-2-5.

Reference Example III-1-A

Substantially the same as the Example III-1, except for the followingchanges:

No nonmetallocene complex was used.

The thus obtained catalyst was named as CAT-II-1-A.

Reference Example III-1-B

Substantially the same as the Example III-1, except for the followingchanges:

The ratio by molar of magnesium chloride to the nonmetallocene complexwas changed to 1:0.16.

The thus obtained catalyst was named as CAT-II-1-B.

Reference Example III-1-C

Substantially the same as the Example III-1, except for the followingchanges:

The ratio by molar of magnesium chloride to the nonmetallocene complexwas changed to 1:0.04.

The thus obtained catalyst was named as CAT-II-1-C.

Reference Example III-1-D

Substantially the same as the Example III-1, except for the followingchanges:

The modified carrier was not treated by titanium tetrachloride.

The thus obtained catalyst was named as CAT-III-1-D.

Reference Example III-1-E

Substantially the same as the Example III-1, except for the followingchanges:

In preparation of the modified carrier, 60 ml hexane was added to themagnesium compound solution to precipitate same, which was thenfiltered, washed with hexane for 3 times (60 ml per time).

The thus obtained catalyst was named as CAT-III-1-E.

Reference Example III-1-F

Substantially the same as the Example III-1, except for the followingchanges:

The nonmetallocene complex was changed to the following nonmetalloceneligand.

The thus obtained catalyst was named as CAT-III-1-F.

Example III-3 Application Example III

The catalysts CAT-III-1, CAT-III-2, CAT-III-1-1 to CAT-III-1-5,CAT-III-2-5, CAT-III-1-A to CAT-III-1-F obtained from the aforesaidExample III series were used for ethylenehomopolymerization/copolymerization and ultra high molecular weightpolyethylene preparation under the following conditions according to thefollowing processes respectively.

Homopolymerization: an autoclave for polymerization (5 L), a slurrypolymerization process, hexane (2.5 L) as the solvent, a totalpolymerization pressure of 0.8 MPa, a polymerization temperature of 85°C., a partial pressure of hydrogen gas of 0.2 MPa, a polymerization timeof 2 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 50 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto, and then hydrogen gas was supplied thereto till 0.2 MPa,and finally ethylene was continuously supplied thereto to keep the totalpolymerization pressure constant at 0.8 MPa. Upon completion of thepolymerization, the inside of the autoclave was vented to theatmosphere, and the resultant polymer product was discharged from theautoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table III-1.

Copolymerization: an autoclave for polymerization (5 L), a slurrypolymerization process, hexane (2.5 L) as the solvent, a totalpolymerization pressure of 0.8 MPa, a polymerization temperature of 85°C., a partial pressure of hydrogen gas of 0.2 MPa, a polymerization timeof 2 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 50 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto. Hexene-1 (50 g) was added thereto all at once as thecomonomer, and then hydrogen gas was supplied thereto till 0.2 MPa, andfinally ethylene was continuously supplied thereto to keep the totalpolymerization pressure constant at 0.8 MPa. Upon completion of thepolymerization, the inside of the autoclave was vented to theatmosphere, and the resultant polymer product was discharged from theautoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table III-1.

Preparation of ultra high molecular weight polyethylene: an autoclavefor polymerization (5 L), a slurry polymerization process, hexane (2.5L) as the solvent, a total polymerization pressure of 0.5 MPa, apolymerization temperature of 70° C., a ratio by molar of theco-catalyst to the active metal in the catalyst of 100, a polymerizationtime of 6 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 50 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto, and finally ethylene was continuously supplied thereto tokeep the total polymerization pressure constant at 0.5 MPa. Uponcompletion of the polymerization, the inside of the autoclave was ventedto the atmosphere, and the resultant polymer product was discharged fromthe autoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table III-2

TABLE III-1 The results of the olefin polymerization obtained with thesupported nonmetallocene catalysts ratio by molar of co-catalyst BulkMolecular Experiment to active Poly activity density weight No. CatalystNo. Co-catalyst metal type (kgPE/gCat) (g/cm³) distribution 1 CAT-III-1triethylaluminum 100 homopolymerization 86.24 0.29 3.20 2 CAT-III-1methylaluminoxane 100 homopolymerization 88.37 0.30 2.77 3 CAT-III-1triethylaluminum 100 copolymerization 95.85 0.30 2.98 4 CAT-III-1triethylaluminum 500 copolymerization 101.12 0.30 3.28 5 CAT-III-1-1triethylaluminum 100 homopolymerization 33.70 0.25 — 6 CAT-III-1-2triethylaluminum 100 homopolymerization 95.24 0.26 — 7 CAT-III-1-3triethylaluminum 100 homopolymerization 44.77 0.26 — 8 CAT-III-1-4triethylaluminum 100 homopolymerization 31.65 0.25 — 9 CAT-III-1-5triethylaluminum 100 homopolymerization 82.90 0.28 — 10 CAT-III-2triethylaluminum 100 homopolymerization 90.27 0.30 2.87 11 CAT-III-2methylaluminoxane 100 homopolymerization 94.35 0.32 2.56 12 CAT-III-2triethylaluminum 100 copolymerization 103.70 0.31 2.95 13 CAT-III-2-1triethylaluminum 100 homopolymerization 47.65 0.26 — 14 CAT-III-2-2triethylaluminum 100 homopolymerization 73.55 0.29 — 15 CAT-III-2-3triethylaluminum 100 homopolymerization 51.82 0.27 — 16 CAT-III-2-4triethylaluminum 100 homopolymerization 38.40 0.27 — 17 CAT-III-2-5triethylaluminum 100 homopolymerization 88.40 0.28 — 18 CAT-III-1-Atriethylaluminum 100 homopolymerization 70.20 0.28 4.14 19 CAT-III-1-Btriethylaluminum 100 homopolymerization 101.50 0.31 2.70 20 CAT-III-1-Ctriethylaluminum 100 homopolymerization 78.74 0.29 3.44 21 CAT-III-1-Dtriethylaluminum 100 homopolymerization 12.56 0.31 2.70 22 CAT-III-1-Etriethylaluminum 100 homopolymerization 80.20 0.31 3.34 23 CAT-III-1-Ftriethylaluminum 100 homopolymerization 43.63 0.28 3.14

TABLE III-2 The results of the ultra high molecular weight polyethylenepreparation obtained with the supported nonmetallocene catalysts PolyExper- activity Bulk Mv iment (kgPE/ density (10⁴ No. Catalyst No.Co-catalyst gCat) (g/cm³) g/mol) 1 CAT-III-1 triethyl aluminum 93.370.34 400 2 CAT-III-1 methyl 80.26 0.34 430 aluminoxane 3 CAT-III-2triethyl aluminum 102.38 0.34 450 4 CAT-III-2 methyl 97.46 0.35 535aluminoxane 5 CAT-III-1-A triethyl aluminum 68.99 0.31 280 6 CAT-III-1-Btriethyl aluminum 98.28 0.33 496 7 CAT-III-1-C triethyl aluminum 77.810.32 375 8 CAT-III-1-D triethyl aluminum 20.68 0.26 240 9 CAT-III-1-Etriethyl aluminum 83.37 0.38 370 10 CAT-III-1-F triethyl aluminum 57.510.30 420

As can be seen from the results of the experiment Nos. 3 and 4 in theTable III-1, increasing the ratio by molar of the co-catalyst to theactive metal in the catalyst will not significantly change thepolymerization activity and the bulk density of the polymer. This factindicates that a high activity for olefin polymerization can be obtainedwith a relatively less amount of the co-catalyst when the supportednonmetallocene catalyst produced in line with the process of thisinvention is used herein.

Upon comparison of the results of the experiment No. 1 and those of theexperiment No. 3, the results of the experiment No. 10 and those of theexperiment No. 12, in the Table III-1, it is clear that in case ofcopolymerization, the polymerization activity increases significantly.This fact indicates that the supported nonmetallocene catalyst producedin line with the process of this invention exhibits a relativelysignificant co-monomer effect.

Upon comparison of the results from the experiment No. 1 and those fromthe reference example experiment Nos. 18 to 20 in the Table III-1, it isclear that the activity of the catalyst increases or decreases as theamount of the nonmetallocene complex to be introduced into the catalystincreases or decreases, while the molecular weight distribution of thepolymer narrows or broadens accordingly. Further, the activity of thecatalyst increases or decreases as the amount of the chemical treatingagent to be introduced into the catalyst increases or decreases, whilethe molecular weight distribution of the polymer broadens or narrowsaccordingly. This fact indicates that the nonmetallocene complex shows afunction of narrowing the molecular weight distribution of the polymer,while the chemical treating agent shows a function of increasing theactivity of the catalyst and broadening the molecular weightdistribution of the polymer. For this reason, different catalysts interms of activity and polymer performances can be obtained with thisinvention by altering the ratio between these two components.

As can be seen from the results of the experiment Nos. 1 to 9 and 10 to16 in the Table III-1, treatment of the modified carrier with theassistant chemical treating agent will increase the activity of thecatalyst and narrow the molecular weight distribution of the polymer.This fact indicates that the assistant chemical treating agent shows afunction of increasing the activity of the catalyst and narrowing themolecular weight distribution of the polymer.

As can be seen from the results of the experiment Nos. 1, 18 and 21 inthe Table III-1 and those of the experiment Nos. 1, 5 and 8 in the TableIII-2, the catalyst obtained with the case wherein only nonmetallocenecomplex was used in preparation of the supported nonmetallocenecatalyst, or that obtained with the case wherein only chemical treatingagent was used in preparation of the supported nonmetallocene catalyst,shows lowered activity than that obtained with the case wherein both ofthe nonmetallocene complex and the chemical treating agent were used inpreparation of the supported nonmetallocene catalyst. This factindicates that the supported nonmetallocene catalyst produced in linewith the process of this invention necessarily involves a synergiceffect. That is, the activity observed with the case wherein bothcomponents exist is higher than that observed with the case wherein onlyeither component exists.

Upon comparison of the results from the experiment No. 1 and those fromthe experiment No. 22 in the Table III-1, it is clear that the catalystobtained by a direct drying process exhibits a significantly higheractivity than that obtained by a filtering, washing and drying process.

Upon comparison of the results from the experiment No. 1 and those fromthe experiment No. 23 in the Table III-1, it is clear that the activityof the catalyst obtained by supporting the nonmetallocene complex issignificantly higher than that of the catalyst obtained by supportingthe nonmetallocene ligand. The reason is that a nonmetallocene ligandper se has no activity for olefin polymerization, and will be given sameonly after in-situ reacting with a chemical treating agent to form anonmetallocene complex.

As can be seen from the Table III-2, it is possible to prepare an ultrahigh molecular weight polyethylene (with to some degree increased bulkdensity) by using the catalyst according to this invention. Uponcomparison of the results from the experiment No. 1 and those from theexperiment No. 2, the results from the experiment No. 3 and those fromthe experiment No. 4, it is clear that the viscosity averaged molecularweight of the polymer can be increased by using MAO as the co-catalyst.Upon comparison of the results from the experiment No. 1 and those fromthe reference example experiment Nos. 5 to 7 in the Table III-2, it isclear that the viscosity averaged molecular weight of the polymerincreases or decreases as the amount of the nonmetallocene complex to beintroduced into the catalyst increases or decreases. This fact indicatesthat the nonmetallocene complex further shows a function of increasingthe viscosity averaged molecular weight of the polymer.

Upon comparison of the results from the experiment No. 1 and those fromthe reference experiment No. 10 in the Table III-2, it is clear that theactivity in preparation of the ultra high molecular weight polyethyleneof the catalyst obtained by supporting the nonmetallocene complex issignificantly higher than that of the catalyst obtained by supportingthe nonmetallocene ligand. The reason is also that a nonmetalloceneligand per se has no activity for olefin polymerization, and will begiven same only after in-situ reacting with a chemical treating agent toform a nonmetallocene complex. Further, in treatment of the modifiedcarrier containing the nonmetallocene ligand with the chemical treatingagent, the in-situ reaction is so violent that the formed structure ofthe modified carrier is destroyed, which leads to a lowered molecularweight of the resultant ultra high molecular weight polyethylene.

Example IV Corresponding to the Fourth Embodiment Example IV-1

Anhydrous magnesium chloride was used as the magnesium compound,tetrahydrofuran was used as the solvent for dissolving the magnesiumcompound and the nonmetallocene complex, titanium tetrachloride was usedas the chemical treating agent, the compound represented by

was used as the nonmetallocene complex.

5 g of the anhydrous magnesium chloride and the nonmetallocene complexwere weighted, tetrahydrofuran was added thereto to completely dissolvesame at the normal temperature. After stirring for 2 hours, hexane (asthe precipitating agent) was added thereto to precipitate same. Theresultant solid was then filtered, washed by a solvent for washing(which is the same as the precipitating agent) for 2 times (by using thesame amount as that of the precipitating agent each time) and thenuniformly heated to 60° C. and vacuum dried, to obtain the modifiedcarrier.

Then, to the modified carrier, 60 ml hexane was added, and then titaniumtetrachloride was dropwise added thereto under stirring over a period of30 minutes. The reaction continued at 60° C. under stirring for 4 hours,then filtered, washed with hexane for 2 times (60 ml each time), andvacuum dried at the normal temperature to obtain the supportednonmetallocene catalyst.

In this example, the ratio of magnesium chloride to tetrahydrofuran was1 mol:210 ml, the ratio by molar of magnesium chloride to thenonmetallocene complex was 1:0.08, the ratio by volume of theprecipitating agent to tetrahydrofuran was 1:1, and the ratio by molarof magnesium chloride to titanium tetrachloride was 1:0.15.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-1.

Example IV-1-1

Substantially the same as the Example IV-1, except for the followingchanges:

The nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to toluene, the precipitating agent was changed tocyclohexane, and the chemical treating agent was changed to zirconiumtetrachloride (ZrCl₄).

In this example, the ratio of the magnesium compound to toluene was 1mol:150 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.15, the ratio by volume of theprecipitating agent to the solvent for dissolving the magnesium compoundand the nonmetallocene complex was 1:2, and the ratio by molar of themagnesium compound to the chemical treating agent was 1:0.20.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-1-1.

Example IV-1-2

Substantially the same as the Example IV-1, except for the followingchanges:

The magnesium compound was changed to anhydrous magnesium bromide(MgBr₂), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to ethyl benzene, the precipitating agent waschanged to cycloheptane, and the chemical treating agent was changed totitanium tetrabromide (TiBr₄).

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:250 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.20, the ratio by volume of theprecipitating agent to the solvent for dissolving the magnesium compoundand the nonmetallocene complex was 1:0.7, and the ratio by molar of themagnesium compound to the chemical treating agent was 1:0.30.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-1-2.

Example IV-1-3

Substantially the same as the Example IV-1, except for the followingchanges:

The magnesium compound was changed to ethoxy magnesium chloride(MgCl(OC₂H₅)), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to xylene, the precipitating agent was changed todecane, and the chemical treating agent was changed to tetraethyltitanium (Ti(CH₃CH₂)₄).

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:300 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.04, the ratio by volume of theprecipitating agent to the solvent for dissolving the magnesium compoundand the nonmetallocene complex was 1:1.5, and the ratio by molar of themagnesium compound to the chemical treating agent was 1:0.05.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-1-3.

Example IV-1-4

Substantially the same as the Example IV-1, except for the followingchanges:

The magnesium compound was changed to butoxy magnesium bromide(MgBr(OC₄H₉)), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to diethyl benzene, and the chemical treating agentwas changed to tetran-butyl titanium (Ti(C₄H₉)₄).

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:400 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.30, and the ratio by molar of themagnesium compound to the chemical treating agent was 1:0.50.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-1-4.

Example IV-1-5

Substantially the same as the Example IV-1, except for the followingchanges:

The magnesium compound was changed to methyl magnesium chloride(Mg(CH₃)Cl), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to chloro toluene, and the chemical treating agentwas changed to tetraethyl zirconium (Zr(CH₃CH₂)₄).

In this example, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.10, and the ratio by molar of themagnesium compound to the chemical treating agent was 1:0.10.

The thus obtained supported nonmetallocene catalyst was named as

Example IV-1-6

Substantially the same as the Example IV-1, except for the followingchanges:

The magnesium compound was changed to ethyl magnesium chloride(Mg(C₂H₅)Cl), the nonmetallocene complex was changed to

and the chemical treating agent was changed to tetraethoxy titanium(Ti(OCH₃CH₂)₄).

The thus obtained supported nonmetallocene catalyst was named as

Example IV-1-7

Substantially the same as the Example IV-1, except for the followingchanges:

The magnesium compound was changed to ethyl magnesium (Mg(C₂H₅)₂), thenonmetallocene complex was changed to

and the chemical treating agent was changed to isobutyl trichlorotitanium (Ti(i-C₄H₉)Cl₃).

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-1-7.

Example IV-1-8

Substantially the same as the Example IV-1, except for the followingchanges:

The magnesium compound was changed to methyl ethoxy magnesium(Mg(OC₂H₅)(CH₃)), and the chemical treating agent was changed totriisobutoxy chloro titanium (TiCl(i-OC₄H₉)₃).

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-1-8.

Example IV-1-9

Substantially the same as the Example IV-1, except for the followingchanges:

The magnesium compound was changed to ethyl n-butoxy magnesium(Mg(OC₄H₉)(C₂H₅)), and the chemical treating agent was changed todimethoxy dichloro zirconium (ZrCl₂(OCH₃)₂).

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-1-9.

Example IV-2

Anhydrous magnesium chloride was used as the magnesium compound,tetrahydrofuran was used as the solvent for dissolving the magnesiumcompound and the nonmetallocene complex, titanium tetrachloride was usedas the chemical treating agent, the compound represented by

was used as the nonmetallocene complex.

5 g of the anhydrous magnesium chloride and the nonmetallocene complexwere weighted, tetrahydrofuran was added thereto to completely dissolvesame at the normal temperature. After stirring for 2 hours, hexane (asthe precipitating agent) was added thereto to precipitate same. Theresultant solid was then filtered, washed by a solvent for washing(which is the same as the precipitating agent) for 2 times (by using thesame amount as that of the precipitating agent each time) and thenuniformly heated to 60° C. and vacuum dried, to obtain the modifiedcarrier.

Then, to the modified carrier, 60 ml hexane was added, and then triethylaluminum (as the assistant chemical treating agent, at a concentrationof 15 wt % in hexane) was dropwise added thereto under stirring over aperiod of 30 minutes. The reaction continued at 60° C. under stirringfor 4 hours, then filtered, washed with hexane for 2 times (60 ml eachtime), and vacuum dried at the normal temperature.

Then, to the thus pre-treated modified carrier, 60 ml hexane was added,and then titanium tetrachloride was dropwise added thereto understirring over a period of 30 minutes. The reaction continued at 60° C.under stirring for 4 hours, then filtered, washed with hexane for 2times (60 ml each time), and vacuum dried at the normal temperature toobtain the supported nonmetallocene catalyst.

In this example, the ratio of magnesium chloride to tetrahydrofuran was1 mol:210 ml, the ratio by molar of magnesium chloride to thenonmetallocene complex was 1:0.08, the ratio by volume of theprecipitating agent to tetrahydrofuran was 1:1, the ratio by molar ofmagnesium chloride to triethyl aluminum was 1:0.15, and the ratio bymolar of magnesium chloride to titanium tetrachloride was 1:0.15.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-2.

Example IV-2-1

Substantially the same as the Example IV-2, except for the followingchanges:

The nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to toluene, the precipitating agent was changed tocyclohexane, the assistant chemical treating agent was changed to methylaluminoxane (MAO, a 10 wt % solution in toluene), and the chemicaltreating agent was changed to zirconium tetrachloride (ZrCl₄).

The magnesium compound solution was vacuum dried at 90° C.

After pre-treated with the assistant chemical treating agent, theresultant was washed with toluene for 3 times.

In this example, the ratio of the magnesium compound to toluene was 1mol:150 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.15, the ratio by volume of theprecipitating agent to the solvent for dissolving the magnesium compoundand the nonmetallocene complex was 1:2, the ratio by molar of themagnesium compound to the assistant chemical treating agent was 1:0.15,and the ratio by molar of the magnesium compound to the chemicaltreating agent was 1:0.20.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-2-1.

Example IV-2-2

Substantially the same as the Example IV-2, except for the followingchanges:

The magnesium compound was changed to anhydrous magnesium bromide(MgBr₂), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to ethyl benzene, the precipitating agent waschanged to cycloheptane, the assistant chemical treating agent waschanged to trimethyl aluminum (Al(CH₃)₃), and the chemical treatingagent was changed to titanium tetrabromide (TiBr₄).

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:250 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.2, the ratio by volume of theprecipitating agent to the solvent for dissolving the magnesium compoundand the nonmetallocene complex was 1:0.70, the ratio by molar of themagnesium compound to the assistant chemical treating agent was 1:0.30,and the ratio by molar of the magnesium compound to the chemicaltreating agent was 1:0.30.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-2-2.

Example IV-2-3

Substantially the same as the Example IV-2, except for the followingchanges:

The magnesium compound was changed to ethoxy magnesium chloride(MgCl(OC₂H₅)), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to xylene, the precipitating agent was changed todecane, the assistant chemical treating agent was changed to triisobutylaluminum (Al(i-C₄H₉)₃), and the chemical treating agent was changed totetraethyl titanium (Ti(CH₃CH₂)₄).

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:300 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.04, the ratio by volume of theprecipitating agent to the solvent for dissolving the magnesium compoundand the nonmetallocene complex was 1:1.5, the ratio by molar of themagnesium compound to the assistant chemical treating agent was 1:0.05,and the ratio by molar of the magnesium compound to the chemicaltreating agent was 1:0.05.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-2-3.

Example IV-2-4

Substantially the same as the Example IV-2, except for the followingchanges:

The magnesium compound was changed to butoxy magnesium bromide(MgBr(OC₄H₉)), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to diethyl benzene, the assistant chemical treatingagent was changed to isobutyl aluminoxane, and the chemical treatingagent was changed to tetran-butyl titanium (Ti(C₄H₉)₄).

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:400 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.30, the ratio by molar of the magnesiumcompound to the assistant chemical treating agent was 1:0.50, and theratio by molar of the magnesium compound to the chemical treating agentwas 1:0.50.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-2-4.

Example IV-2-5

Substantially the same as the Example IV-2, except for the followingchanges:

The magnesium compound was changed to methyl magnesium chloride(Mg(CH₃)Cl), the solvent for dissolving the magnesium compound and thenonmetallocene complex was changed to chloro toluene, the assistantchemical treating agent was changed to diethyl methyl aluminum(Al(CH₃)(CH₃CH₂)₂), and the chemical treating agent was changed totetraethyl zirconium (Zr(CH₃CH₂)₄).

In this example, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.10, the ratio by molar of the magnesiumcompound to the assistant chemical treating agent was 1:0.10, and theratio by molar of the magnesium compound to the chemical treating agentwas 1:0.10.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-2-5.

Reference Example IV-1-A

Substantially the same as the Example IV-1, except for the followingchanges:

No nonmetallocene complex was used.

The thus obtained catalyst was named as CAT-IV-1-A.

Reference Example IV-1-B

Substantially the same as the Example IV-1, except for the followingchanges:

The ratio by molar of magnesium chloride to the nonmetallocene complexwas changed to 1:0.16.

The thus obtained catalyst was named as CAT-IV-1-B.

Reference Example IV-1-C

Substantially the same as the Example IV-1, except for the followingchanges:

The ratio by molar of magnesium chloride to the nonmetallocene complexwas changed to 1:0.04.

The thus obtained catalyst was named as CAT-IV-1-C.

Reference Example IV-1-D

Substantially the same as the Example IV-1, except for the followingchanges:

The modified carrier was not treated by titanium tetrachloride.

The thus obtained catalyst was named as CAT-IV-1-D.

Reference Example IV-1-E

Substantially the same as the Example IV-1, except for the followingchanges:

The nonmetallocene complex was changed to the following nonmetalloceneligand.

The thus obtained catalyst was named as CAT-IV-1-E.

Example IV-3 Application Example IV

The catalysts CAT-IV-1, CAT-IV-2, CAT-IV-1-1 to CAT-IV-1-5, CAT-IV-2-5,CAT-IV-1-A to CAT-IV-1-E obtained from the aforesaid Example IV serieswere used for ethylene homopolymerization/copolymerization and ultrahigh molecular weight polyethylene preparation under the followingconditions according to the following processes respectively.

Homopolymerization: an autoclave for polymerization (5 L), a slurrypolymerization process, hexane (2.5 L) as the solvent, a totalpolymerization pressure of 0.8 MPa, a polymerization temperature of 85°C., a partial pressure of hydrogen gas of 0.2 MPa, a polymerization timeof 2 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 50 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto, and then hydrogen gas was supplied thereto till 0.2 MPa,and finally ethylene was continuously supplied thereto to keep the totalpolymerization pressure constant at 0.8 MPa. Upon completion of thepolymerization, the inside of the autoclave was vented to theatmosphere, and the resultant polymer product was discharged from theautoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table IV-1.

Copolymerization: an autoclave for polymerization (5 L), a slurrypolymerization process, hexane (2.5 L) as the solvent, a totalpolymerization pressure of 0.8 MPa, a polymerization temperature of 85°C., a partial pressure of hydrogen gas of 0.2 MPa, a polymerization timeof 2 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 50 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto. Hexene-1 (50 g) was added thereto all at once as thecomonomer, and then hydrogen gas was supplied thereto till 0.2 MPa, andfinally ethylene was continuously supplied thereto to keep the totalpolymerization pressure constant at 0.8 MPa. Upon completion of thepolymerization, the inside of the autoclave was vented to theatmosphere, and the resultant polymer product was discharged from theautoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table IV-1.

Preparation of ultra high molecular weight polyethylene: an autoclavefor polymerization (5 L), a slurry polymerization process, hexane (2.5L) as the solvent, a total polymerization pressure of 0.5 MPa, apolymerization temperature of 70° C., a ratio by molar of theco-catalyst to the active metal in the catalyst of 100, a polymerizationtime of 6 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 50 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto, and finally ethylene was continuously supplied thereto tokeep the total polymerization pressure constant at 0.5 MPa. Uponcompletion of the polymerization, the inside of the autoclave was ventedto the atmosphere, and the resultant polymer product was discharged fromthe autoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table IV-2.

TABLE IV-1 The results of the olefin polymerization obtained with thesupported nonmetallocene catalysts ratio by molar of co-catalyst BulkMolecular Experiment to active Poly activity density weight No. CatalystNo. Co-catalyst metal type (kgPE/gCat) (g/cm³) distribution 1 CAT-IV-1triethylaluminum 100 homopolymerization 80.20 0.31 3.34 2 CAT-IV-1methylaluminoxane 100 homopolymerization 82.18 0.32 2.92 3 CAT-IV-1triethylaluminum 100 copolymerization 89.14 0.32 3.07 4 CAT-IV-1triethylaluminum 500 copolymerization 94.04 0.32 3.40 5 CAT-IV-1-1triethylaluminum 100 homopolymerization 31.34 0.27 — 6 CAT-IV-1-2triethylaluminum 100 homopolymerization 62.54 0.28 — 7 CAT-IV-1-3triethylaluminum 100 homopolymerization 41.64 0.28 — 8 CAT-IV-1-4triethylaluminum 100 homopolymerization 29.43 0.27 — 9 CAT-IV-1-5triethylaluminum 100 homopolymerization 77.10 0.30 — 10 CAT-IV-2triethylaluminum 100 homopolymerization 82.41 0.32 2.96 11 CAT-IV-2methylaluminoxane 100 homopolymerization 87.75 0.34 2.75 12 CAT-IV-2triethylaluminum 100 copolymerization 96.44 0.33 3.05 13 CAT-IV-2-1triethylaluminum 100 homopolymerization 44.31 0.28 — 14 CAT-IV-2-2triethylaluminum 100 homopolymerization 68.40 0.31 — 15 CAT-IV-2-3triethylaluminum 100 homopolymerization 48.19 0.29 — 16 CAT-IV-2-4triethylaluminum 100 homopolymerization 35.71 0.29 — 17 CAT-IV-2-5triethylaluminum 100 homopolymerization 82.21 0.30 — 18 CAT-IV-1-Atriethylaluminum 100 homopolymerization 65.29 0.30 4.21 19 CAT-IV-1-Btriethylaluminum 100 homopolymerization 94.40 0.33 2.86 20 CAT-IV-1-Ctriethylaluminum 100 homopolymerization 73.23 0.31 3.57 21 CAT-IV-1-Dtriethylaluminum 100 homopolymerization 11.47 0.27 2.40 22 CAT-IV-1-Etriethylaluminum 100 homopolymerization 56.82 0.29 3.26

TABLE IV-2 The results of the ultra high molecular weight polyethylenepreparation obtained with the supported nonmetallocene catalysts Exper-Poly Bulk Mv iment activity density (10⁴ No. Catalyst No. Co-catalyst(kgPE/gCat) (g/cm³) g/mol) 1 CAT-IV-1 triethyl 83.37 0.38 370 aluminum 2CAT-IV-1 methyl 71.66 0.38 400 aluminoxane 3 CAT-IV-2 triethyl 91.410.38 425 aluminum 4 CAT-IV-2 methyl 87.02 0.39 522 aluminoxane 5CAT-IV-1-A triethyl 54.47 0.35 280 aluminum 6 CAT-IV-1-B triethyl 87.750.37 484 aluminum 7 CAT-IV-1-C triethyl 67.74 0.35 300 aluminum 8CAT-IV-1-D triethyl 16.40 0.31 585 aluminum 9 CAT-IV-1-E triethyl 60.570.33 390 aluminum

As can be seen from the results of the experiment Nos. 3 and 4 in theTable IV-1, increasing the amount of the co-catalyst to be used (i.e.increasing the ratio by molar of the co-catalyst to the active metal inthe catalyst) will not significantly change the polymerization activityand the bulk density of the polymer. This fact indicates that a highactivity for olefin polymerization can be obtained with a relativelyless amount of the co-catalyst when the supported nonmetallocenecatalyst produced in line with the process of this invention is usedherein.

Upon comparison of the results of the experiment No. 1 and those of theexperiment No. 3, the results of the experiment No. 10 and those of theexperiment No. 12 in the Table IV-1, it is clear that in case ofcopolymerization, the polymerization activity increases significantly.This fact indicates that the supported nonmetallocene catalyst producedin line with the process of this invention exhibits a relativelysignificant co-monomer effect.

Upon comparison of the results from the experiment No. 1 and those fromthe reference example experiment Nos. 18 to 20 in the Table IV-1, it isclear that the activity of the catalyst increases or decreases as theamount of the nonmetallocene complex to be introduced into the catalystincreases or decreases, while the molecular weight distribution of thepolymer narrows or broadens accordingly. Further, the activity of thecatalyst increases or decreases as the amount of the chemical treatingagent to be introduced into the catalyst increases or decreases, whilethe molecular weight distribution of the polymer broadens or narrowsaccordingly. This fact indicates that the nonmetallocene complex shows afunction of narrowing the molecular weight distribution of the polymer,while the chemical treating agent shows a function of increasing theactivity of the catalyst and broadening the molecular weightdistribution of the polymer. For this reason, different catalysts interms of activity and polymer performances can be obtained with thisinvention by altering the ratio between these two components.

As can be seen from the results of the experiment Nos. 1 to 9 and 10 to16 in the Table IV-1, treatment of the modified carrier with theassistant chemical treating agent will increase the activity of thecatalyst and narrow the molecular weight distribution of the polymer.This fact indicates that the assistant chemical treating agent shows afunction of increasing the activity of the catalyst and narrowing themolecular weight distribution of the polymer.

Upon comparison of the results from the experiment No. 1 and those fromthe reference example experiment No. 21 in the Table IV-1, the resultsfrom the experiment No. 1 and those from the reference exampleexperiment No. 8 in the Table IV-2, it is clear that the chemicaltreatment will significantly increase the activity of the catalyst.

Upon comparison of the results from the experiment No. 1 and those fromthe reference example experiment No. 22 in the Table IV-1, just asrevealed by the Table III-1, it is clear that the activity of thecatalyst obtained by supporting the nonmetallocene complex issignificantly higher than that of the catalyst obtained by supportingthe nonmetallocene ligand. The reason is also that a nonmetalloceneligand per se has no activity for olefin polymerization, and will begiven same only after in-situ reacting with a chemical treating agent toform a nonmetallocene complex.

As can be seen from the Table IV-2, it is possible to prepare an ultrahigh molecular weight polyethylene (with to some degree increased bulkdensity) by using the catalyst according to this invention. Uponcomparison of the results from the experiment No. 1 and those from theexperiment No. 2, the results from the experiment No. 3 and those fromthe experiment No. 4, it is clear that the viscosity averaged molecularweight of the polymer can be increased by using MAO as the co-catalyst.Upon comparison of the results from the experiment No. 1 and those fromthe reference example experiment Nos. 5 to 8 in the Table IV-2, it isclear that the viscosity averaged molecular weight of the polymerincreases or decreases as the amount of the nonmetallocene complex to beintroduced into the catalyst increases or decreases. This fact indicatesthat the nonmetallocene complex further shows a function of increasingthe viscosity averaged molecular weight of the polymer.

As can be seen from the results of the experiment Nos. 1, 18 and 21 inthe Table IV-1 and those of the experiment Nos. 1, 5 and 8 in the TableIV-2, the catalyst obtained with the case wherein only nonmetallocenecomplex was used in preparation of the supported nonmetallocenecatalyst, or that obtained with the case wherein only chemical treatingagent was used in preparation of the supported nonmetallocene catalyst,shows lowered activity than that obtained with the case wherein both ofthe nonmetallocene complex and the chemical treating agent were used inpreparation of the supported nonmetallocene catalyst. This factindicates that the supported nonmetallocene catalyst produced in linewith the process of this invention necessarily involves a synergiceffect. That is, the activity observed with the case wherein bothcomponents exist is higher than that observed with the case wherein onlyeither component exists.

Upon comparison of the results from the experiment No. 1 and those fromthe reference example experiment No. 9 in the Table IV-2, it is clearthat the activity in preparation of the ultra high molecular weightpolyethylene of the catalyst obtained by supporting the nonmetallocenecomplex is significantly higher than that of the catalyst obtained bysupporting the nonmetallocene ligand. The reason is also that anonmetallocene ligand per se has no activity for olefin polymerization,and will be given same only after in-situ reacting with a chemicaltreating agent to form a nonmetallocene complex. Further, in treatmentof the modified carrier containing the nonmetallocene ligand with thechemical treating agent, the in-situ reaction is so violent that theformed structure of the modified carrier is destroyed, which leads to alowered molecular weight of the resultant ultra high molecular weightpolyethylene.

It will be apparent to those skilled in the art that variousmodifications and variation can be made in the present invention withoutdeparting from the spirit or scope of the invention. Thus, it isintended that the present invention cover the modifications andvariations of this invention provided they come within the scope of theappended claims and their equivalents.

1-15. (canceled)
 16. A process for producing a supported nonmetallocenecatalyst, comprising the steps of: dissolving a magnesium compound and anonmetallocene complex in a solvent, to obtain a magnesium compoundsolution; and drying the magnesium compound solution, or introducinginto the magnesium compound solution a precipitating agent, to obtainthe supported nonmetallocene catalyst.
 17. A process for producing asupported nonmetallocene catalyst, comprising the steps of: dissolving amagnesium compound and a nonmetallocene complex in a solvent, to obtaina magnesium compound solution; drying the magnesium compound solution,or introducing into the magnesium compound solution a precipitatingagent, to obtain a modified carrier; and treating the modified carrierwith a chemical treating agent selected from the group consisting of aGroup IVB metal compound to obtain the supported nonmetallocenecatalyst.
 18. The process according to claim 17, further comprising thestep of pre-treating the modified carrier with an assistant chemicaltreating agent selected from the group consisting of an aluminoxane, analkylaluminum and any combination thereof before treating the modifiedcarrier with the chemical treating agent.
 19. The process according toclaim 16 or 17, wherein the magnesium compound is one or more selectedfrom the group consisting of a magnesium halide, an alkoxy magnesiumhalide, an alkoxy magnesium, an alkyl magnesium, an alkyl magnesiumhalide and an alkyl alkoxy magnesium.
 20. The process according to claim19, wherein the magnesium compound is one or more selected from thegroup consisting of a magnesium halide.
 21. The process according toclaim 16 or 17, wherein the solvent is one or more selected from thegroup consisting of a C₆₋₁₂ aromatic hydrocarbon, a halogenated C₆₋₁₂aromatic hydrocarbon, an ester and an ether.
 22. The process accordingto claim 21, wherein the solvent is one or more selected from the groupconsisting of a C₆₋₁₂ aromatic hydrocarbon and tetrahydrofuran.
 23. Theprocess according to claim 16 or 17, wherein the nonmetallocene complexis one or more selected from the group consisting of the compoundshaving the following structure,

wherein, q is 0 or 1; d is 0 or 1; m is 1, 2 or 3; M is selected fromthe group consisting of a Group III to XI metal atom in the PeriodicTable of Elements; n is 1, 2, 3 or 4, depending on the valence of thecentral metal atom M; X is selected from the group consisting of ahalogen atom, a hydrogen atom, a C₁-C₃₀ hydrocarbyl, a substitutedC₁-C₃₀ hydrocarbyl, an oxygen-containing group, a nitrogen-containinggroup, a sulfur-containing group, a boron-containing group, analuminium-containing group, a phosphor-containing group, asilicon-containing group, a germanium-containing group, and atin-containing group, when multiple Xs exist, the Xs may be the same asor different from one another, and may form a bond or a ring with oneanother; A is selected from the group consisting of an oxygen atom, asulfur atom, a selenium atom,

—NR²³R²⁴, —N(O)R²⁵R²⁶,

—PR²⁸R²⁹, —P(O)R³⁰OR³¹, a sulfone group, a sulfoxide group and—Se(O)R³⁹, wherein N, O, S, Se and P each represents a coordinationatom; B is selected from the group consisting of a nitrogen atom, anitrogen-containing group, a phosphor-containing group and a C₁-C₃₀hydrocarbyl; D is selected from the group consisting of a nitrogen atom,an oxygen atom, a sulfur atom, a selenium atom, a phosphor atom, anitrogen-containing group, a phosphor-containing group, a C₁-C₃₀hydrocarbyl, a sulfone group, a sulfoxide group,

—N(O)R²⁵R²⁶,

and —P(O)R³²(OR³³), wherein N, O, S, Se and P each represents acoordination atom; E is selected from the group consisting of anitrogen-containing group, an oxygen-containing group, asulfur-containing group, a selenium-containing group, aphosphor-containing group and a cyano group, wherein N, O, S, Se and Peach represents a coordination atom; G is selected from the groupconsisting of a C₁-C₃₀ hydrocarbyl, a substituted C₁-C₃₀ hydrocarbyl andan inert functional group; → represents a single bond or a double bond;— represents a covalent bond or an ionic bond; - - - represents acoordination bond, a covalent bond or an ionic bond; R¹ to R³, R²² toR³³, and R³⁹ are each independently selected from the group consistingof a hydrogen atom, a C₁-C₃₀ hydrocarbyl, a substituted C₁-C₃₀hydrocarbyl and an inert functional group, wherein these groups may beidentical to or different from one another, and any adjacent groups mayform a bond or a ring with one another.
 24. The process according toclaim 23, wherein the nonmetallocene complex is one or more selectedfrom the group consisting of the following compound (A) and thefollowing compound (B),

wherein, F is selected from the group consisting of a nitrogen atom, anitrogen-containing group, an oxygen-containing group, asulfur-containing group, a selenium-containing group and aphosphor-containing group, wherein N, O, S, Se and P each represents acoordination atom.
 25. The process according to claim 24, wherein thenonmetallocene complex is one or more selected from the group consistingof the following compound (A-1), the following compound (A-2), thefollowing compound (A-3), the following compound (A-4), the followingcompound (B-1), the following compound (B-2), the following compound(B-3), and the following compound (B-4),

wherein, Y is selected from the group consisting of an oxygen atom, anitrogen-containing group, an oxygen-containing group, asulfur-containing group, a selenium-containing group and aphosphor-containing group, wherein N, O, S, Se and P each represents acoordination atom; Z is selected from the group consisting of anitrogen-containing group, an oxygen-containing group, asulfur-containing group, a selenium-containing group, aphosphor-containing group and a cyano group, wherein N, O, S, Se and Peach represents a coordination atom; R⁴, and R⁶ to R²¹ are eachindependently selected from the group consisting of a hydrogen atom, aC₁-C₃₀ hydrocarbyl, a substituted C₁-C₃₀ hydrocarbyl and an inertfunctional group, wherein these groups may be identical to or differentfrom one another, and any adjacent groups may form a bond or a ring withone another; and R⁵ is selected from the group consisting of the lonepair electron on the nitrogen atom, a hydrogen atom, a C₁-C₃₀hydrocarbyl, a substituted C₁-C₃₀ hydrocarbyl, an oxygen-containinggroup, a sulfur-containing group, a nitrogen-containing group, aselenium-containing group, and a phosphor-containing group, with theproviso that when R⁵ is the oxygen-containing group, thesulfur-containing group, the nitrogen-containing group, theselenium-containing group or the phosphor-containing group, N, O, S, Pand Se in the group R⁵ each can act as a coordination atom to coordinatewith the central metal atom (the Group IVB metal atom).
 26. The processaccording to claim 25, wherein, the halogen atom is selected from thegroup consisting of F, Cl, Br and I, the nitrogen-containing group isselected from the group consisting of

—NR²³R²⁴, -T-NR²³R²⁴ and —N(O)R²⁵R²⁶, the phosphor-containing group isselected from the group consisting of

PR²⁸R²⁹, —P(O)R³⁰R³¹ and —P(O)R³²(OR³³), the oxygen-containing group isselected from the group consisting of hydroxy, —OR³⁴ and -T-OR³⁴, thesulfur-containing group is selected from the group consisting of —SR³⁵,-T-SR³⁵, —S(O)R³⁶ and -T-SO₂R³⁷, the selenium-containing group isselected from the group consisting of —SeR³⁸, -T-SeR³⁸, —Se(O)R³⁹ and-T-Se(O)R³⁹, the group T is selected from the group consisting of aC₁-C₃₀ hydrocarbyl, a substituted C₁-C₃₀ hydrocarbyl and an inertfunctional group, R³⁷ is selected from the group consisting of ahydrogen atom, a C₁-C₃₀ hydrocarbyl, a substituted C₁-C₃₀ hydrocarbyland an inert functional group, the C₁-C₃₀ hydrocarbyl is selected fromthe group consisting of a C₁-C₃₀ alkyl group, a C₇-C₅₀ alkylaryl group,a C₇-C₅₀ aralkyl group, a C₃-C₃₀ cyclic alkyl group, a C₂-C₃₀ alkenylgroup, a C₂-C₃₀ alkynyl group, a C₆-C₃₀ aryl group, a C₈-C₃₀ fused-ringgroup and a C₄-C₃₀ heterocycle group, wherein the heterocycle groupcontains 1 to 3 hetero atom(s) selected from the group consisting of anitrogen atom, an oxygen atom and a sulfur atom, the substituted C₁-C₃₀hydrocarbyl is selected from the group consisting of the C₁-C₃₀hydrocarbyl having one or more substituent(s) selected from the halogenatom and the C₁-C₃₀ alkyl group, the inert functional group is selectedfrom the group consisting of the halogen atom, the oxygen-containinggroup, the nitrogen-containing group, a silicon-containing group, agermanium-containing group, the sulfur-containing group, atin-containing group, a C₁-C₁₀ ester group and a nitro group, theboron-containing group is selected from the group consisting of BF₄ ⁻,(C₆F₅)₄B⁻ and (R⁴⁰BAr₃)⁻, the aluminium-containing group is selectedfrom the group consisting of an alkyl aluminium, AlPh₄ ⁻, AlF₄ ⁻, AlCl₄⁻, AlBr₄ ⁻, AlI₄ ⁻ and R⁴¹AlAr₃ ⁻, the silicon-containing group isselected from the group consisting of —SiR⁴²R⁴³R⁴⁴, and -T-SiR⁴⁵, thegermanium-containing group is selected from the group consisting of—GeR⁴⁶R⁴⁷R⁴⁸, and -T-GeR⁴⁹, the tin-containing group is selected fromthe group consisting of —SnR⁵⁰R⁵¹R⁵², -T-SnR⁵³ and -T-Sn(O)R⁵⁴, the Argroup represents a C₆-C₃₀ aryl group, R³⁴ to R³⁶, R³⁸ and R⁴⁰ to R⁵⁴ areeach independently selected from the group consisting of a hydrogenatom, the C₁-C₃₀ hydrocarbyl, the substituted C₁-C₃₀ hydrocarbyl and theinert functional group, wherein these groups may be identical to ordifferent from one another, and any adjacent groups may form a bond or aring with one another, and the group T is defined as aforesaid.
 27. Theprocess according to claim 16 or 17, wherein the nonmetallocene complexis one or more selected from the group consisting of the followingcompounds,


28. The process according to claim 16, wherein ratio by molar of themagnesium compound (based on Mg) to the nonmetallocene complex is1:0.01-1, ratio of the magnesium compound to the solvent is 1 mol:75˜400ml, and ratio by volume of the precipitating agent to the solvent is1:0.2˜5.
 29. The process according to claim 16 or 17, wherein theprecipitating agent is one or more selected from the group consisting ofan alkane, a cyclic alkane, a halogenated alkane and a halogenatedcyclic alkane.
 30. The process according to claim 29, wherein theprecipitating agent is one or more selected from the group consisting ofhexane, heptane, decane and cyclohexane.
 31. The process according toclaim 17, wherein ratio by molar of the magnesium compound (based on Mg)to the nonmetallocene complex is 1:0.01-1, ratio of the magnesiumcompound to the solvent is 1 mol:75˜400 ml, ratio by volume of theprecipitating agent to the solvent is 1:0.2˜5, and ratio by molar of themagnesium compound (based on Mg) to the chemical treating agent (basedon the Group IVB metal) is 1:0.01-1.
 32. The process according to claim17, wherein the Group IVB metal compound is one or more selected fromthe group consisting of a Group IVB metal halide, a Group IVB metalalkylate, a Group IVB metal alkoxylate, a Group IVB metal alkyl halide,and a Group IVB metal alkoxy halide.
 33. The process according to claim32, wherein the Group IVB metal compound is one or more selected fromthe group consisting of a Group IVB metal halide.
 34. The processaccording to claim 18, wherein the aluminoxane is one or more selectedfrom the group consisting of methyl aluminoxane, ethyl aluminoxane,isobutyl aluminoxane and n-butyl aluminoxane, and the alkylaluminum isone or more selected from the group consisting of trimethyl aluminum,triethyl aluminum, tripropyl aluminum and triisobutyl aluminum.
 35. Theprocess according to claim 18, wherein ratio by molar of the magnesiumcompound (based on Mg) to the assistant chemical treating agent (basedon Al) is 1:0-1.0.
 36. A supported nonmetallocene catalyst, produced inline with the process according to claim 16 or
 17. 37. An olefinhomopolymerization/copolymerization process, wherein the supportednonmetallocene catalyst according to claim 36 is used as the maincatalyst, in combination of one or more selected from the groupconsisting of an aluminoxane, an alkylaluminum, a halogenated alkylaluminum, a fluoroborane, an alkylboron and an alkylboron ammonium saltas the co-catalyst, for homopolymerization or copolymerization of theolefin.